(C C Addison) Inorganic Chemistry of The Main-Gro

A Specialist Periodical Report
Inorganic Chemistry of the Main-group

Elements
Volume 2
A Review of the Literature Published between

September 1972 and September 1973
Senior Reporter
C. C. Addison
Reporters
M. G. Barker
G. Davidson
M. F. A. Dove
P. G. Harrison
P. Hubberstey
A. Morris
R. J. Pulham
D. B. Sowerby
All of: Deportment of Chemistry, Univeisity of Nottinghani
@ Copyright 1974
The Chemical Society

Burlington House, London WIV OBN
ISBN :0 85186 762 6

Library of Congress Catalog Card No 72-95098
Printed in Northern Ireland at The Universities Press, Belfast.
Preface
The framework used in Volume 1 for reporting the Chemistry of the Maingroup Elements appears to have been generally acceptable, and has been
continued in Volume 2. The present volume therefore comprises eight
chapters, each concerned with one of the Main Groups as defined in the
abbreviated form of the Periodic Table given in the Preface to Volume 1, and
it has now been agreed that the chemistry of zinc, cadmium, and mercury will
be included in the Specialist Periodical Reports concerned with the Transition
Elements.
The relative sizes of the chapters are much the same as in Volume 1 and this
again reflects the amount of published research in each Group. In Chapter 1,
greater coverage is given to those properties of the metals which are relevant
to their use in the generation of electrical energy from batteries, or from
nuclear fission and fusion reactors, and both Chapters 1 and 2 include more
illustrative material. Chapter 3 reflects a steady increase in effort throughout
the Group, but an especially large number of papers have been published on
carbaborane r-complexes. Chapter 4 is large, consistent with the considerable
amount of research which continues to be published on each of these elements.
Chapter 5 now includes a short section on nitrogen oxides and atmospheric
chemistry, but the bulk of published material is again concerned with the
chemistry of phosphorus; there are some 500 references to phosphorus,
whereas arsenic, antimony, and bismuth together are covered by 240
references. Careful selection has been necessary in Chapter 6 to avoid overlap
with other chapters or volumes. Thus, this chapter contains the chemistry of
sulphides of Main-group elements, but not sulphides of transition metals.
Again, S-N compounds are dealt with in this chapter, whereas S-B compounds are in Chapter 3, and S-P and S-As compounds in Chapter 5. The
halides of the elements are treated as they arise in Chapters 1-6, and Chapter
7 is restricted to interesting recent developments in halogen chemistry, such
as the superacids. Noble-gas chemistry is represented by a small number of
highly interesting papers, which are discussed in Chapter 8.
We have continued the policy of referring to physical properties (and
particularly spectroscopic data) of compounds only where this is essential to
demonstrate some important chemical property, Similarly, we refer only to
those aspects of organo-derivatives which illustrate significant features in the
chemistry of the Main-group element involved. On the other hand, more
structures are becoming available (often highly refined) now that X-ray
diffraction methods are becoming computerized; the chemistry becomes more
meaningful, and is more readily explained, once the structure is known, and
other physical measurements become less significant. We have therefore taken
every opportunity to include structures of key compounds.
The whole volume is again written by members of the Department of
Chemistry in the University of Nottingham, so that the maximum degree of
...
111
iv
Preface
consultation has been possible. In spite of this, and in spite of the fact that the
period of coverage of Volume 2 is from September 1972 to September 1973
(i.e. 12 months as against 15 months for Volume l), Volume 2 is appreciably
longer. This is not due entirely to the enthusiasm of the authors; with experience, it has become easier to identify developing themes, and to discuss
them meaningfully, and we have the impression that the amount of research
effort devoted to the Main-group elements is increasing.
C . C. Addison
Contents
Chapter 1 Elements of Group I
By R. I. Pulhom
Introduction
The Alkali Metals
Alloys and Intermetallic Compounds
11
Solvation of Alkali-metal Ions

Aqueous Solvation
Non-aqueous Solvation
13
13
17
5 Compounds containing Organic Molecules or Complex

25
Ions
6 Alkali-metal Oxides
34
7 Alkali-metal Halides
38
8 Lithium Compounds
42
9 Sodium Compounds
49
10 Potassium Compounds
53
11 Rubidium Compounds
56
12 Caesium Compounds
57
13 Analysis
58
14 Molten Salts
60
61
64
Nitrates
Halides
Chapter 2 Elements of Group I I
73
By R. J. Pulham
Beryllium
73
Magnesium
77
Calcium
86
Strontium
92
Barium
95
6 Analysis
99
V
vi
Contents
Chapter 3 Elements of Group Ill
103
By G. Davidson
1 Boron
103
103
General
1 04
Boron Hydrides
110
Borane Anions and their Derivatives
Carbaboranes and their Metallo-derivatives
117
Aminoboranes and other Compounds containing B- -N
139
Bonds
144
Compounds containing B-P or B-As Bonds
Boron Halides
147
151
Compounds containing B-0 Bonds
158
Compounds containing B-C Bonds
160
Boron-containing Heterocycles
170
Compounds containing B-S Bonds
171
Boron Nitride and Metal Borides
2 Aluminium
General and Analytical
Aluminium Hydrides
Compounds containing AI-C and Al-Si Bonds
Compounds containing Al-N Bonds
Compounds containing A1-0 or AI-S Bonds
Aluminium Halides
Other Aluminium Compounds
174
174
174
177
179
183
193
198
3 Gallium
199
199
199
201
204
206

Compounds containing Ga-N
Compounds containing Ga-0
Gallium Halides
Other Gallium Compounds
Bonds
or Ga-S
Bonds
4 Indium
207
207
Compounds containing In-0, In-S, or In-Se Bonds 208
Indium Halides
212
Other Indium Compounds
215
5 Thallium
Thallium(1n) Compounds
Thalliurn(1) Compounds
Other Thallium Compounds
216
216
217
219
224
vi i
Contents
Chapter 4 Elements of Group IV
225
By P. G. Harrison and P. Hubberstey
1 Carbon
225
Allotropes
225
Vapour-phase Species
226
Diamond
227
Graphite
228
Vitreous Carbon
230
Carbyne
230
Carbon Fibres
230
Surface, Adsorption, and Catalytic Studies
23 1
Oxidation Studies
232
Carbides
235
Graphite Intercalation Compounds
238
Alkali Metals.
239
Halogens, Halides, Oxides, and Acids
240
Methane and its Substituted Derivatives
242
Methane
242
Halogenomethanes
245
Other Substituted Methanes
254
Formaldehyde and its Substituted Derivatives
260
Formaldehyde, Thioformaldehyde, Carbonyl Halides, and Thiocarbonyl Halides
260
Formic Acid and Formates
263
Derivatives of Group VI Elements
265
Oxides, Sulphides, and Related Species
265
Carbonates, Thiocarbonates, and Related Anions 276
Derivatives of Group V Elements
28 1
Cyanogen and Cyanides
28 1
Cyanates and Related Species
287
2 Silicon, Germanium, Tin, and Lead
Hydrides of Silicon, Germanium, Tin, and Lead
Halides of Silicon, Germanium, Tin, and Lead
Synthesis
Reactions of Silicon, Germanium, and Tin Tetrahalides and Related Compounds
Physical Studies of Quadrivalent Silicon, Germanium, and Tin Halides
(i) Structural studies
(ii) Infrared, Raman, and microwave data
(iii) N.m.r. studies
(iv) Mossbauer studies
290
290
297
297
301
304
304
305
306
306
viii
Contents
(v) Miscellaneous studies
Complexes and Complex Anions
(i) Halide donors
(ii) Oxygen donors
(iii) Sulphur donors
(iv) Nitrogen donors
(v) Phosphorus donors
Oxygen Derivatives of Silicon, Germanium, Tin, and
Lead
Silicon Solid-state Chemistry
(i) Silicon Dioxide
(ii) Silicates
(iii) Aluminosilicates
(iv) Zeolites
Germanium(1v) Oxide and Germanates
Tin(rv) Oxide and Stannates
Lead(xv) Oxide and Plumbates
Molecular Oxides
Alkoxides
Carboxylates
Oxyacid Derivatives
Miscellaneous Derivatives
Silicon, Germanium, Tin, and Lead Derivatives of
Sulphur, Selenium, and Tellurium
Thio-germanates, -stannates, and -plumbates, and
Related Systems
Molecular Compounds containing M-S, -Se, and
-Te (M = Si, Ge, Sn, or Pb) Bonds
Compounds containing Silicon-, Germanium-, Tin-,
and Lead-Nitrogen Bonds
Phosphorus and Arsenic Derivatives of Silicon,
Germanium, and Tin.
Pseudohalide Derivatives of Silicon, Germanium, and
Tin.
Derivatives containing Silicon-, Germanium-, and
Tin-Main-group Metal Bonds
Bonds to Group IV Metals
Bonds to Group 111 Metals
Transition-metal Derivatives of Silicon, Germanium,
Tin, and Lead
Bivalent Derivatives of Silicon, Germanium, Tin, and
Lead
Sily lenes
Germanium(n), Tin@), and Lead(@ Halides and
Halide Complexes
307
307
307
308
3 14
3 14
315
315
316
316
324
336
341
350
352
353
354
358
362
364
367
369
369
370
372
382
382
383
383
386
388
402
402
405
ix
Contents
Oxygen Derivatives of Germanium(Ir), Tin(@, and
Lead(1x)
Compounds containing Silicon(1x)-, Germanium(II)-, Tin@)-, and Lead@)-Chalcogenide
Bonds
Lead@) Pseudohalides
OrganometallicDerivativesof Bivalent Germanium,
Tin, and Lead
Complexation Behaviour of Lead@) in Aqueous
Media
Catalytic Activity of Silicon- and Tin-containing
Systems
Miscellaneous Physical Measurements
Intermetallic Phases
Binary Systems
Ternary Systems
Chapter 5 Elements of Group V
408
413
417
41 8
421
422
424
424
424
427
430
By A. Morris and D. 6.Sowerby
1 Nitrogen
Elementary Nitrogen
Bonds to Hydrogen
NH and NH, Compounds
NH3 and Derivatives
NH; Compounds
N,H, and Derivatives
Bonds to Carbon
Bonds to Nitrogen
Bonds to Oxygen
N2O
NO
Nitrogen(II1) Species
NOz-NZO4
Nitric Acid
Nitrates
Miscellaneous N-0 Species
Nitrogen Oxides and Atmospheric Chemistry
Bonds to Fluorine
NF,-N,F,
Miscellaneous N-F Species
Bonds to Chlorine and Iodine
2 Phosphorus
Element
Phosphides
Hydrides
430
430
433
433
434
440
442
444
447
450
450
452
454
455
457
459
46 1
462
464
464
465
466
466
466
467
469
Contents
Bonds to Boron
Bonds to Carbon
Phosphorus(rrr) Compounds
Phosphorus(v) Compounds
Bonds to Silicon, Germanium, or Tin
Bonds to Halogens
Phosphorus(II1) Halides
Phosphorus(v) Halides
Compounds containing P-C Bonds
Compounds containing P-0 Bonds
Compounds containing P-S Bonds
Bonds to Nitrogen
Phosphorus(Ir1) Compounds
Pseudohalides
Compounds containing P-N-P
Bonds
Compounds containing P,N, Rings
Phosphonitriles (Phosphazenes)
Heteroatom Ring Systems
Bonds to Oxygen
Lower Oxidation States
Heteropolyacids
Monophosphates
Apatites
Diphosphates
Meta- and Poly-phosphates
Bonds to Sulphur or Selenium
470
472
472
475
479
480
480
482
485
489
493
493
493
495
501
501
503
504
512
5 14
514
516
518
519
522
523
524
528
3 Arsenic
Element and Arsenides
Bonds to Carbon
Arsenic(Ii1) Compounds
Arsenic(v) Compounds
Bonds to Halogen
Bonds to Nitrogen
Bonds to Oxygen
532
532
533
533
535
537
538
539
542
Antimony
General
Bonds to Halogen
Antimony(1Ir) Compounds
Antimony(v) Compounds
Bonds to Oxygen
545
545
546
546
549
552
554
xi
Contents
5 Bismuth
General
Bonds to Halogens
Bonds to Oxygen
Chapter 6 Elements of Group VI
555
555
556
557
558
560
By M . G. Barker
1 Oxygen
The Element
Ozone
Ion Species
Oxygen Fluorides
Water
560
560
562
565
567
568
2 Sulphur
The Element
Sulphides
Sulphides of Group I, 11, and I11 Metals
Group IV Metal Sulphides
Group V Metal Sulphides
Other Metal Sulphides
Ternary Sulphide Phase Systems
Ternary Sulphide Compounds
Polysulphide Ions
Hydrogen Sulphide
Sulphur-Halogen Compounds
Sulphur-Oxygen-Halogen Compounds
Sulphur-Nitrogen Compounds
Linear Compounds
Ring Compounds
Sulphur-Nitrogen-Phosphorus Compounds
Sulphur-Boron Ring Compounds
Sulphur-Oxygen Compounds
Sulphur Dioxide
Sulphur Trioxide
Sulphates
Alkali-metal Sulphates
Alkaline-earth-metal Sulphates
0ther Metal Sulphates
Spectra and Pha'se Diagrams of Sulphate Systems
Fluorosulphates
Sulphites
572
572
575
516
578
580
584
584
585
588
589
591
593
596
596
599
604
605
605
606
608
608
610
61 1
612
612
61 3
614
Contents
xii
Sulphuric Acid and Related Systems
Other Sulphur-containing Compounds
3 Selenium
The Element
The Oxides of Selenium
Selenium-Halogen Compounds
Selenides
Group PI1 Element Selenides
Group IV Element Selenides
Group V Element-Selenium Compounds
Selenates
Selenites
Other Compounds of Selenium
4 Tellurium
The Element
Tellurium-Oxygen Compounds
Tellurium-Halogen Compounds
Compounds with a Te- Bond
Tellurides
5 Polonium
Chapter 7 The Halogens and Hydrogen
616
617
619
619
620
62 1
624
624
625
627
628
631
633
635
635
636
639
644
648
649
650
By M . F. A. Dove
1 Halogens
Elements
Halides
Interhalogens and Related Compounds
Oxide Halides
Compounds with Oxygen
Hydrogen Halides
2 Hydrogen
Protonic Acid Media
Hydrogen-bonding
Miscellaneous
650
650
656
657
663
664
669
672
672
673
675
Contents
xiii
Chapter 8 The Noble Gases

By M. F. A. Dove
676
1 The Elements
676
2 Argon, Krypton, and Xenon@)
676
3 Xenon(1v)
678
4 Xenon(v1)
679
5 Xenon(vIr1)
683
Author Index
684
Elements of Group I
~~~~
BY R. J. PULHAM
1 Introduction
In this chapter individual references which are inter-related are grouped

together to make a section and, therefore, reference to several alkali metals
may feature in a single section. Each reference, however, appears once only
within this chapter so that, if described in one section, it will not be duplicated
in any other. Single references to topics are presented systematically in the
section on the appropriate metal.
The elements of Groups I and I1 are so closely linked in some instances
that a section describing them jointly is presented to avoid duplication in
Chapter 2. Such a case is the section on Molten Salts, which covers the
chemistry of the molten salts of both Groups I and I1 but is presented only
in this chapter.
2 The Alkali Metals
The hyperfine structure of the 1 sn 3P terms of singly ionized lithium -6,
-7 (Li 11) has been investigated by the beam-foil technique. Zero-field
quantum beats were observed in the intensity decays of transitions from the
1 sn 3P terms (n = 2, 3, or 4) in 6*7LiI1 and the magnetic hyperfine coupling
constant was determined for each isotope for the 2p 3P terms. Preliminary
values for the coupling constants are A (1s2p 3P,6Li11) = 0.091 f 0.001 cm-l
(2.73 GHz), A(ls,2p 3P, Li 11) = 0.239 f 0.002 cm-l (7.17 GHz). The
measured fine structures agree within a few percent with recent ca1culations.l
The Auger electron spectrum of freshly filed lithium contains an emission
peak at 51.7 eV which is attributed to the KL,L, Auger transition, and unidentified peaks at 27.5 and 8 eV. On exposure to oxygen the peaks at 51.7
and 27.5 eV disappeared but the 8 eV peak intensified. The low-energy
spectrum was characterized by emissions at 13.3, 24.0, 33.0, and 40.0 eV due
to Auger transitions of lithium, oxygen, and lithium monoxide.2 A value of
3.05 eV is reported for the work function of freshly prepared lithium films.3
a
H. G . Berry, J. L. Subtil, E. H. Pinnington, H. J. Andrae, W. Wittmann, and A.

Gaupp, P h p . Rev. (A), 1973,7, 1609.
R. E. Clausing, D. S. Easton, and G . L. Powell, Surface Sci., 1973, 36, 377.
J. Boesenberg, Phys. Letters (A), 1972, 41, 185.
Inor,oanic Chemistry of the Main-group Elements
Lithium, the not so rare metal, is reviewed. The discussion covers the
. ~ metal
occurrence, production, and LISGS of the irietal and its c o m p o ~ n d sThe
has considerable potential in the future generation of electrical energy from
the fusion reaction:
?H
+ :H
---f
:He
+ 17.6 MeV
The supply of tritium for this process is derived from:
Within this context, the chemical, physical, and thermal properties of

lithium that are related to its use in fusion reactors have been reviewed.
These include natural abundance, thermodynamic and transport properties,
characterization, analysis purity control, and corrosion of materials by the
molten liquid5 Problems associated with tritium in the metal are also covered,,
as is the separation of tritium from lithium by crystallization or diffusion.
The pressures of hydrogen isotopes in equilibrium with their solutions in
liquid lithium have been measured. The square root of the hydrogen pressure
is proportional to the hydrogen concentration in accordance with Sieverts
Law. Graphical data are presented for 2H.8The metal is also chemically very
reactive. The effect of temperature and pressure on the reaction of static
molten lithium with oxygen, nitrogen, and the compounds CCl,F,, C,F,,
and SF, has been studied, The metal is hsated inductively under vacuum and a
small known volume of gas exposed to the surface. Pressure and temperature
changes are followed by rapid-response instr~mentation.~
The liquid metal
is a versatile solvent for both non-metals and metals. Non-metals when
dissolved in the metal may not have the same deleterious corrosive effect on
containment materials as they do with sodium. Chemical processes are
affected by the different thermodynamic stability of lithium compounds. This
is illustrated by the effect of oxygen on the chemical corrosion of niobium
and tantalum by static liquid lithium at 600 C in capsules. An increase in
the oxygen concentration of lithium from 100 to 2000 p.p.m. has no measurable effect, a result which is contrary to the effect of similar oxygen concentrations in liquid sodium or potassium. The free energy of formation of
lithium oxide is so great that the liquid metal getters niobium and tantalum to
an oxygen level 120p.p.m. regardless of the oxygen concentration in the
lithium. When the transition metals contain more than a threshold level of
oxygen (400 and 100 p.p.m. for Nb and Ta respectively), chemical attack by
lithium occurs at the grain boundaries with the formation of ternary compounds containing lithium, oxygen, and transition metal.1 Methods of
R. Feather, Philippine Geogr. J., 1973, 17, 16.
V. A. Maroni, E. J. Cairns, and F. A. Cafasso, ANL-8001 Rept. 1973.
R. G. Hickman, UCRL-74057 Rept., 1972.
H. Weichselgartner, Reaktortagung, 1972, 751.
* D. H. J. Goodall and G. M. McCracken, Proc. Symp. Fusion Technol., 7 t h , 1972, p. 151.
T. E. Little, U. S. Nat. Tech. Inform. Serv. AD Rept, 1972, No. 759378.
lo R. L. Klueh, ORNL-TM-4069 Rept., 1973.
ti
Elements of Group I
analysing the liquid are obviously important. Photon activation appears

applicable for the analysis of nitrogen and oxygen. These elements are determined by photon activation with a microtron as a pray source. The 13Nis
separated by distillation as ammonia and collected in sulphuric acid for
activity measurements. Oxygen is rapidly separated by distillation as water
wt % for each element.11*12
for coincidence counting. Sensitivity is 2 x
In addition to its role in the fusion reactor, liquid lithium features prominently in solid-state batteries,13an area which has been reviewed.14 Lithium and
another element are usually separated by a solid or liquid electrolyte permeable to lithium ions, which migrate to form a compound with anions of the
second element, thus driving electrons through the external circuit. The
second element has been halogen, though this may be replaced by a compound,
e.g. vanadium pent0~ide.l~
Present interest is in the chalcogens, and several
lithium-chalcogen systems have been investigated with this use in mind.
Equilibrium phases in the Li-S system on the sulphur side of Li2S (the only
compound observed) are determined by using an unusual vapour-transport
technique. By this means equilibrium compositions of the melts at various
temperatures can be obtained by utilizing the transport of sulphur vapour
from one melt to another. The Li-S phase diagram exhibits a large miscibility
gap which extends from the monotectic composition, 65.5 mol % S , to
almost pure sulphur (0.035 mol % Li) at the monotectic temperature 362 f
3 "C. The m.p. of Li2S is 1365 f 10 "C.16This is largely corroborated by a
second study which gives the miscibility gap from 63 to 98.8 mol % S, the
monotectic at 364.8 'C, the m.p. of Li2Sas 1372 "C,and a critical temperature
for the miscibility gap of >600 "C?' An e.m.f. method using cells of the type
LilLi halide eutectic mixturelLi in selenium is used to determine thermodynamic quantities in the lithium-selenium system. From the cell data the
standard free energy of formation of Li,Se at 360 "C is calculated as -94.0
kcal mol-l.ls In the Li-Te phase diagram, eutectics occur at 179.9 "C near
the lithium axis at >99.0 atom % Li, 448.5 "C at 35.7 atom % Li, and 423.1
"C at 10.5 atom % Li. Two intermediate compounds are present, Li,Te and
LiTe,, melting at 1204.5 and 459.9 "C, respe~tive1y.l~
The spectrum of doubly ionized sodium I11 has been studied at 25001300 A and the analysis has been revised and extended as regards the 2p44s,
B. A. Chapyzhnikov, Kh. N. Evzhanov, E. D. Malikova, L. L. Kunin, and V. N.
Samosyuk, Radiochem. Radioanalyt. Letters, 1972, 11, 269.
la B. A. Chapyzhnikov, Kh. N. Evzhanov, E. D. Malikova, L. L. Kunin, and V. N.
Samosyuk, Radiochem. Radioanalyt. Letters, 1972, 11, 275.
l3 M. Eisenberg, Intersoc. Energy Convers. Eng. Conf., Con$ Proc. 7th, 1972, 75.
lo B. Scrosati, J. Appl. Electrochem., 1972,2,231.
A. N. Dey, Ger. Offen. 2 155 890 (C1. H O h ) , 17 May 1973.
l6 R. A. Sharma, J. Electrochem. Soc., 1972, 119, 1439.
l7 P. T. Cunningham, S. A. Johnson, and E. J. Cairns, J . Electrochem. SOC.,1972,119,
1448.
I* E. J. Cairns, G. H. Kucera, and P. T. Cunningham, J. Electrochem. SOC.,1973,120,
595.
P. T. Cunningham, S. A. Johnson, and E. J. Cairns, J. Electrochem. SOC.,
1973, 120,
328.
l1
Inorganic Chemistry of the Main-group Elements
3p, and 3d configurations. The number of classified lines is now 177, out of
which 110 are newly observed and Classified. Some of the older classifications
are altered and ca. 80 lines rejected as spurious. The following terms and
levels are new: (T)4s4P, 2P; (1D)4S2&,2; (lS)4s2S, (10)3p2F, 20,2P;
(lS)3p2P;(3P)3d4F;(3P)3d4P,4F5/2;and (1D)2G, 2F, 2D3/2.The 2p43s, 3p, 3d4s
configurations are now complete.20In the range 380-18OA about 90 lines
are measured, of which 50 are reported for the first time.21The third, fourth,
and fifth (i.e. Na IV, Na V, and Na VI) spark spectra of sodium have been
re-photographed at 80-2400 A and the ineasurements confirm earlier
analyses.22New lines in Na IV, Na V, and Na VI are observed for the
first time and ~ l a s s i f i e dThe
. ~ ~ K X-ray spectra of sodium excited by protons,
helium, and oxygen ions of 0.8, 3.2, and 30 MeV, respectively, have been
measured. The strongest lines are the normal K, satellite spectra produced by
multiple electron vacancies in single ion-atom collisions. In the H- and Heion-induced spectra, Ka1,2is the strongest transition.24On the absorption side,
the spectrum of atomic sodium between 30 and 150 eV shows lines which can
be attributed to the excitation of a 2s or 2p electron. Considerably broad and
asymmetric absorptions above the lP1series limit are due to the simultaneous
excitation of a 2p and 3s electron.25
The electrical conductivity of sodium vapour has been measured in a
coaxial-cylinder, two-electrode system at 827-1 227 "C.The results support
the conductivities calculated by E. J. Robbins et al. (1967, 1968) on the basis
of a model for the vapour consisting of Na,, Na,, and Na, moieties.26The
concentration of multi-atom associates in saturated vapours at various
temperatures can be semi-empirically derived. In the case of unsaturated
vapours, the number of associates tends to zero with increasing size. The
symmetry of the associates, binding energies, and mobility for sodium and
potassium are given. The effect of temperature is calculated on the equilibrium between the concentration of free sodium atoms and those combined
in the cluster. Agreement with experimental data is sati~factory.~'
The best
available thermodynamic data on liquid metals are tabulated and include
m.p., entropies of fusion, heats of fusion, and heat capacities. Graphical
correlations are presented between heats of fusion and melting points, and
between entropies of fusion and structural parameters. Heat-capacity
anomalies are discussed in terms of the electron configuration of the metal.2a
The surface tensions of molten alkali metals from their melting temperatures
22
23
24
25
26
27
28
L. Minnhagen and H. Nietsche, Physica Scripta, 1972, 5 , 237.

T. Lundstrom and L. Minnhagen, Physica Scripta, 1972, 5 , 243.
T. Goto, M. S. Gautam, and Y. N. Joshi, Physica, 1973, 66, 70.
T. Goto, M. S. Gautam, and Y. N. Joshi, Canad. J . Phys., 1973, 51, 1244.
C. F. Moore, D. K. Olsen, B. Hodge, and P. Richard, Z.Physik, 1972, 257, 288.
H. W. Wolff, K. Radler, B. Sonntag, and R. Haensel, Z. Physik, 1972, 257, 353.
R. Morrow and J. D. Craggs, J . Pliys. (D),
1973, 6, 1274.
V. G. Klyuchnikov and L. A. Borovinskii, Sbornik. Issled. Striikt. Mol. Krist. Krist.,
Zarodyshei, 1971, 57.
J. L. Margrave, CoIlog. Int. Cent. Nat. Rech. Sci.,1972, No. 205, p. 71.
Elements of Group I
up to 1127 "C have been determined in a special high-temperature, highpressure apparatus. The surface tensions/dyn cm-l as a function of temperature (t/"C) under an atmosphere of their own vapours are given by:
7Na =
193.6 - 0.094(t - 98)
107.1 - 0.069(t - 64)

= 85.7 - 0.053(t - 38)
YI; =
YRb
yCs = 68.8
- 0.045(t
- 28)
The values correlate well with those previously p u b l i ~ h e d . ~ ~

As with lithium, the majority of the literature on the commercial uses of
metallic sodium is devoted to aspects of the generation of electrical energy
either where the metal is used as a coolant in fast nuclear reactors or used as
an electrode in high-power batteries. An indication of the extent of the
nuclear use of liquid sodium is provided in a review of the principal programmes involving fast reactors in the
Technological aspects are also
repre~ented?l-~*These applications steadily reveal new chemical properties
of sodium and its compounds, This is illustrated in the proceedings of a
conference on the Liquid Alkali Metals which covers fundamental chemistry,
physics, analytical and instrumentation techniques, sodium-water reactions,
carbon and fission-product behaviour in sodium, physical processes, corrosion, and mass transfer.35Also, chemical reactions in liquid alkali metals are
discussed, with particular emphasis on solvation aspects. A comparison is
made of the nature and properties of liquid metals, representing continuous
reaction media, with other non-aqueous solvents, e g . molecular liquids,
representing discontinuous media.36Chemical aspects are generally found in
the purification, analysis, and corrosion areas. The non-metals oxygen ,
hydrogen, nitrogen, and carbon, when dissolved in the liquid metal, have a
deleterious effect on transition metals, which are invariably employed as
containment rnaterial~.~'Purification and analytical techniques, therefore,
are primarily designed to remove38and m o n i t ~ r ~these
~ * *elements,
~
in many
cases in sit^.^^ To prevent nitriding and embrittlement of steel submerged in
liquid sodium, ca. 1 atom % calcium or magnesium can be added to the
29
30
31
32
33
34
35
36
37
38
39
40
A. N. Solov'ev and A. A. Kiriyanenko, Fiz. Khim. Poverkh. Yavlenii Vys. Temp.

1971, 108.
M. Grenon, Rev. Fr. Energ., 1972, 23, 577.
F. Chaminade, FRNC-CONF-38 Rept. 1972.
Sodium Technology, 1948-1961 [TID-3334 (Pt. l)]. 1972.
D. W. Shannon and W. R. Wykoff, Nuclear Engineering Internat., 1972, 17, 627.
M. E. Durham, RD/B/M-2479 Rept. 1972.
Proceedings of the International Conference of the BNES, London, on Liquid Alkali
Metals at Nottingham University 4-6 April, 1973.
C . C. Addison, Sci. Progr. (London), 1972, 60, 385.
K. Furukawa, Genshiryoku Kogyo, 1973, 19, 22.
W. Staubwasser, Ger. P. 1 583 891 (CI. C 22b), 28 Jun 1973.
K. L. Schillings, Reaktortagung, 1972,449.
L. F. Lust, F. A. Scott, and J. F. Jarosch, HEDL-TME-71-17 Rept. 1971.
Inorganic Chemistry of the Maimgroup Elements
liquid. These metals, with their strong chemical affinity for nitrogen, effectively isolate the steel from nitrogenjl To analyse for hydrogen in liquid
sodium, a nickel thimble is immersed in the liquid and evacuated to
Torr on the inside. The process relies on the equilibrium between
dissolved and gaseous H. Hydrogen leaves the liquid, diffuses through the
nickel, and establishes an equilibrium pressure, the magnitude of which is
dependent on its concentration in the liquid. As little as 0.02 f 0.01 p.p.m.
of hydrogen can be detected.42Hydrogen may exist in a sample of sodium in
several forms, i.e. dissolved sodium hydride, solid sodium hydride, or sodium
hydroxide. To distinguish between these requires several processes. All the
hydrogen is released as gas by vacuum fusion in a bath of tin at 35OoC.
Amalgamation of the sample, however, releases only dissolved hydrogen.
Subsequent heating to 200 "C decomposes solid sodium hydride. The remaining hydroxide hydrogen may be determined by difference.43Alternatively, the
remaining sodium amalgam is heated in an argon stream at 400 "C. Under
these conditions sodium reacts with sodium hydroxide to give hydrogen,
NaH, and Na,O. Hydride decomposes to give hydrogen, which is determined
by gas ~hromatography?~
Hydrogen is also soluble in liquid potassium. Over
the temperature range 3 4 0 4 4 0 O C , the solubility is given by the equation:
log(C/p.p.m. by wt.) = 6.8 - 2930/(T/K)
The pressure of hydrogen in equilibrium with the saturated solution of
hydrogen in the metal is given by:
log(P/Torr) = 11.3 - 5860/(T/K)
These pressures are the dissociation pressures of potassium hydride according
to:
KH = K
+ *H,
The enthalpy of formation, AH', of potassium hydride as derived from these

pressures is -13.7 kcal mol-l. The equilibrium pressures of hydrogen above
unsaturated solutions of the gas in the metal are given by:
P112 = C x 104/14.2
where C is in weight %. Thus Sieverts' Law is obeyed (I'll2 z C), which
indicates that the species of hydrogen in the metal is m~natomic.*~
Most interest has centred on solutions of oxygen in liquid sodium since
this element, more than any other, renders the liquid metal corrosive.
41
43
44
45
A. K. Fischer, U.S.P. 3 745 068 (CI. 176-38, B O l j , G21c), 10 Jul 1973.

D. R. Vissers, J. T. Holmes, and P. A. Nelson, U.S. P. 3 731 523 (Cl. 73/19; G Oln),
8 May 1973.
Kh. Evzhanov, E. D. Malikova, and L. L. Kunin, Z h r . nnalit. Khim., 1973, 28, 235.
M. Takahashi, J. Nuclear Sci. Technol., 1973, 10, 54.
M. N. Arnol'dov, M. N. Ivanovskii,V. A. Morozov, S. S. Pletenets, and V. V. Sitnikov,
Izvest. Akad. Nauk. S.S.S.R., Metal., 1973, 74.
Elements of Group I
Vanadium, niobium, and tantalum, and their alloys, have a low intrinsic
soIubility in liquid sodium and suffer but slight corrosion. The presence of
oxygen in the liquid, however, leads to penetration by non-metals into the
transition metal, internal oxidation, oxide scale formation, spallation or
dissolution of oxides, and, in some cases, penetration by the sodium.4G
Whether the transition-metal surface oxidizes or whether sodium extracts the
oxygen contained in or on the metal depends largely on the relative free
energies of formation of the transition-metal oxide and sodium oxide,
respectively. The situation is more complicated, however, since the energy
balance is affected by the activity (or concentration) of oxygen in the sodium
or in the solid metal, i.e. a dilute solution of oxygen in liquid sodium may be
reducing whereas a more concentrated solution will oxidize a particular
transition-metal surface. Further complications arise when ternary compounds form which are stable in sodium. Most transition metals form at least
one ternary oxide with sodium. These points are illustrated below. Vanadium,
exposed at 600 OC to static sodium solutions containing oxygen up to 4000
p.p.m. , getters all oxygen from solutions which contain less than 2000 p.p.m.
The distribution coefficient for oxygen between vanadium and sodium is
greater than lo4 at 600C. By alloying chromium or molybdenum with
vanadium, the activity coefficient of oxygen in the solid alloy is increased
and hence the solubility is reduced.47 In sodium containing 2000 p.p.m.
oxygen at 600 O C , alloys of vanadium containing titanium or zirconium form
internal precipitates of oxide during the gettering, and the concentration of
oxygen dissolved in the alloy approaches that of the same alloy without
titanium or zirconium.48 When titanium and zirconium are immersed in
liquid sodium containing dissolved sodium oxide at 600 "C, the surfaces are
covered with the ternary oxides Na,Ti04 and Na,ZrO,, respectively. These
compounds were identified in situ by their X-ray diffraction patterns. The
compound Na4Ti04 was detected when the sodium contained from 100 to
12 000 p.p.m. oxygen. At the end of long contact times the oxide Ti0 formed
below the ternary oxide, which suggests that the ternary oxide is formed
first and is followed by diffusion of oxygen into the substrate metal to form
TiO. With zirconium, a rapid formation of the oxide ZrO, is postulated which
is followed by a slow reaction with dissolved sodium monoxide to give Na,Q,
Zr0,.49 Liquid potassium, like sodium, also becomes more corrosive towards
transition metals when it contains dissolved oxygen. Analysis of potassium
after immersion of tantalum at 600, 800, and 1000 "C shows that the amount
of tantalum finding its way into the alkali metal increases with the amount of
oxygen originally dissolved in the liquid metal. Again, a ternary oxide phase
is formed. Oxygen held in the tantalum also promotes corrosion when the
transition metal contains more than a threshold concentration of oxygen in
46
47
48
49
H. U. Borgstedt and G. Frees, Rev. Coatings Corrosion, 1972, 1, 43.

R. L. Klueh and J. H. DeVan, J. Less-Common Metals, 1973,30,9.
R. L. Klueh and J. H. DeVan, J. Less-Common Metals, 1973,30, 25.
M. G. Barker and D. J. Wood, J.C.S. Dalton, 1972,2451.
solid solution; potassium penetrates the solid metal intergranularly and transgranularly via ternary oxide formation. The threshold levels of oxygen for
this type of attack at 400, 800, and 1000C are 500, 700, and lOOOp.p.m.,
respe~tively.~~
Distribution of radioactive corrosion products is obviously
important in flowing sodium. Particulate material deposits according to flow
rate and geometry of circuit, size of particulate, and whether the species is
soluble in the sodium or reacts preferentially with metallic parts of the circuit.
Initial experiments have investigated the transport and deposition characteristics of 59Fe,54Mn,and 6oCo. The 59Febehaviour is characterized by its
appearance as a firmly adherent layer on pipework downstream of the test
section. 6oCois similar to iron but the deposit is less strongly attached. The
behaviour of 54Mn is characterized by its rapid and highly preferential
migration to the coldest part of the circuit.51 Adsorption of caesium, a
product of the fission process, also occurs from solution in sodium at transition-metal surfaces. Between 100 and 200C, caesium is adsorbed on to
nickel and steel (EN-58B) surfaces but at 800 O C the adsorption is eliminated
The mechanism of adsorption is not clear.52
Determinations of the solubility of oxygen in liquid sodium are numerous
and the values vary. From 169 individual analyses, data have been selected,
therefore, to derive the mean solubility relationship:
log(S/p.p.m.) = 6.1587
- 2386.4/(T/K)
from T = 387 to 828 K, using the least-squares method. This equation is

recommended for fast-reactor
Methods of determining these small
concentrations differ widely. Thus at 350-530 O C , the solubility is ca.
10-850 p.p.m. as determined by an e.m.f. method using the cell:
where the rare-earth oxides comprise the solid electrolyte which separates
the reference electrode Cu,OICu(or air]Au) from the second electrode, a
mixture of sodium with sodium monoxide.54Alternatively, a vanadium wire
is immersed in the molten sodium to allow oxygen to partition between the
two metals. The wire is subsequently removed and analysed for oxygen
content. The method relies on a knowledge of the equilibrium distribution
coefficient of oxygen between sodium and vanadium. These values (as
W.
oxygen in V) are given at 750 OC over the range 0.003-16 p.p.m.
oxygen in sodium.55
Carbon dissolves in liquid sodium but to a lesser extent than do hydrogen
or oxygen, and methods for determining the carbon content of liquid sodium
continuously are generally less advanced than those for oxygen and hydrogen.
50
61
52
53
54
55
R. L. Klueh, Corrosion (Houstom), 1972, 28, 360.

K. T. Claxton and J. G. Collier, J. Brit. Nuclear Energy SOC.,1973, 12, 63.
H. E. Evans and W. R. Watson, RD/B/N-2094 Rept. 1971.
J. D. Noden, J . Brit. Nuclear Energy SOC.,1973, 12, 57.
H. U. Borgstedt, A. Marin, Z . Peric, and G. Wittig, Atomwirt, Atomtech., 1972, 17,
361.
D. L. Smith and R. H. Lee, ANL-7891 Rept. 1972.
Elements of Group I
A technique, reminiscent of the electrochemical oxygen meter, is described,

however, which equilibrates the carbon dissolved in liquid sodium with a
membrane of a-iron at 500-700 "C. This membrane forms part of an electrochemical cell and is separated from a reference source of carbon by a fused
electrolyte of 1 :1 Li,CO,-Na,CO,, which is able to transfer carbon in ionic
form. The voltage between the membrane and reference electrode gives a
measure of carbon activity in the membrane and hence in the sodium.56
Protection and security measures against accidents with liquid sodium are
reviewed.57 A fire-extinguishing powder that is especially effective against
alkali-metal fires consists of 45.4% NH4H,P04 (fluidized with up to 6 %
of its weight by Si02 and silicone resin), 45.4% urea, 9.1 % polystyrene
micro-balls (d < 300 pm), and 0.1 % azodicarbamide; it completely extinguishes sodium burning at >5OO0C. A thick spongy carbonized coating
covers the metal, whose temperature falls very rapidly.58
~ - ~ ~ liquid sodium
High-temperature (300 "C) storage b a t t e r i e ~ ~involving
utilize the chemical reactions between sodium and liquid sulphur. The
Na-S system is complex, however, and contains several polysulphides with
the general formula M,S, containing S",- ions. Of about 15 polysulphides of
the alkali metals described in the literature, the crystal structures have been
determined for only about three, which reflects the difficulty of preparing single
crystals of the polysulphides. The Na,S-Na,S,-S
region has been investigated
mainly by high-temperature microscopy but some complementary experiments involve d.t.a., t.a., and quenching techniques, The components S and
Na,S melt at 118 f 1 "C and 1168 f 10 'C, respectively. The intermediate
phases Na2S2,Na2S4,and Na,S5 which are formed melt at 478 f 5,294 f 2,
and 270 f 5 "C, respectively. Na,S, melts incongruently. The shapes of
polysulphide crystals appearing just below the melting points are detected
by high-temperature micro~copy.~~
Further d.t.a. work reveals that when
Na,S-Na,S, or Na4S4-S, mixtures are heated, a reaction occurs near the
m.p. of sulphur with formation of Na,S5 as the initial step, Unless the S:Na
ratio is >5:2 then further reaction between the sulphides occurs, until at
equilibrium only those species are observed corresponding to the given Na:S
ratio. The highest sulphide is Na,S,, and Na,S, does not exist at the m.p.;
this stoicheiometry is really a 1 :1 Na,S,-Na,S, eutecticBgThe sodium polysulphides Na,S, and Na2S5,however, can be prepared from the reaction of
56
57
58
59
6o
61
62
63
64
65
M. R. Hobdell and D. M. J. Rowe, RD/B/N-2240 Rept. 1972.

M. De la Torre Cabezas, Energ. Niicl. (Madrid), 1972, 16, 439.
E. Chahvekilian, R. Peteri, and A. Hennequart, Fr. Demande 2 102 424 (Cl. A 6 2 4 ,
12 May 1972.
J. Fally, C. Lasne, and Y. Lazennec, Fr. Demande 2 142 695 (CI. H Olm), 9 Mar 1973.
S. Gratch, J. V. Petrocelli, R. P. Tischer, R. W. Minck, and T. J. Whalen, Zntersac.
Energy Convers. Eng. Con$ Con5 Proc. Ith, 1972, p. 38.
T. Nakabayashi, Ger. Offen. 2 240 278 (CI. H Olm),12 Apr 1973, Japan.
J. Fally and J. Richez, Fr. Demande 2 140 318 (C1. H Olrn), 23 Feb 1973.
C. Levine, Power Sources Symp., Proc., 1972, 25, 75.
S. P. Mitoff, U.S. P. 3 672 994 (CI. 136-6, H Olrn), 27 Jun 1972.
E. Rosen and R. Tegman, Chemica Scripta, 1972,2,221.
D. G. Oei, Znorg. Chem., 1973, 12,435.
10
Iiiorganic Chemistry of the Main-group Elements
sodium chloride with K2S, and K,S, respectively in liquid ammonia. Using
KZSG, however, the only polysulphide obtained is Na,S,. The physical
properties of the polysulphides are obviously important in their application
to batteries. Thus the density and surface tension of liquid Na,S, and Na,S,
have been determined as a function of temperature. The unbranched chain
structure of the polysulphide linkage is confirmed by photoelectron spectro~ c o p ySodium
. ~ ~ tetrasulphide, Na,S,, is in fact tetragonal, with space group
142d and cell dimensions a = 9.5965, c = 11.7885 A, and 2 = 8. The structure is built up of unbranched and separated Si- ions surrounded by Na+ ions.
Adjacent SZ- ions are ca. 3.60 A apart. Each lies on a two-fold axis and the
S-C bond distances are 2.074 (end) and 2.061 A (middle). The S-S bond
angle is 109.76' and the dihedral angle is 97.81'. The co-ordination of sulphur around the sodium consists of two types: a distorted tetrahedral
arrangement of sulphur atoms with two pairs at 2.826 and 2.842A from a
central sodium atom; a sodium atom at the centre of a distorted octahedron
with three pairs of sulphur atoms at distances 2.887, 3.043, and 3.081 A,
respectively, from the sodium.G8The monosulphide, Na2S, forms several
hydrates, the stabilities of which depend on the temperature and partial
pressure of water vapour above the compounds. By thermally decomposing
Na2S,9H20the compound Na2S,M,0 was found to be stable over the largest
pressure and temperature range, with an enthalpy of hydration of 16.62 kcal
mol-l. Heats of hydration were lower for the di- and tri-hydrate, being 6.76
and 1.96 kcal mol-l, respe~tively.~~
The spectrum of doubly ionized rubidium (Rb 111) over the range 3703500 A has been re-analysed. The existing analysis is revised and extended.
Most levels of the 5s6s5p4d and 5d configurations are now known.70A second
analysis yields most of the levels of the 4p44d,4p55s, and 4p45pconfigurations.
The ionization energy is estimated as 39.0 f 0.3 eV.'l The vapour pressure of
liquid rubidium from 129 to 278 "C has been determined by thermogravimetric and mass-spectrometric techniques. Calculation of the latent heat of
vaporization from the vapour-pressure data yields a value of 19.0 f 0.5
kcal (g atom)-l at 298 K. The dissociation energy of the Rbz molecule is
10.0 f 0.5 kcalm01-l.~~Both rubidium and caesium have relatively high
vapour pressures which pose experimental problems in the handling of these
elements. The saturated vapour pressures, of R b at 683-1649OC and
0.97-101.5 atm and of Cs at 775-1600 O@ and 2.14-80.5 atm, are given by:
log(Pab/atm) = 5.25903 - 4035.65/(T/K)
- 0.35387 log(T/K)
log(Pcslatm) = 5.71084 - 3904,34/(T/K) - 0.52605 log(T/K)
and
The P,, and P,, curves intersect at 1160 "C and 21.48 atm.73
67
68
ge
70
71
72
73
D. G. Oei, Inorg. Chem., 1973, 12,438.

R. Tegman, Acta Cryst., 1973,29B, 1463.
R. C. Kerby and M. R. Hughson, Canad,, Mines Br., Res. Rep., 1973, NO.262.
J. E. Hansen, W. Persson, and S. Valind, Phys. Letters (A), 1972, 42, 275.
J. Reader and G . L. Epstein, J. Opt. SOC.Amer., 1972, 62, 1467.
V. Piacente, G. Bardi, and L. Malaspina, J. Chem. Thermodynamics, 1973, 5 , 219.
L. I. Cherneeva and V. N. Proskurin, Teplofiz. Vys. Temp., 1972, 10, 765.
Elements of Group I
11
3 Alloys and Intermetallic Compounds

The crystal structure of Li,CdPb is f.c.c., with a = 6.837 A, d(expt) = 6.79 at
20 ' C , and d(X-ray) = 6.93 for 2 = 4. The observed and calculated X-ray
intensities are tabulated. The most probable space group is T$ - F 4 3 m 7 ,
The Li-Ga phase diagram, when investigated by d.t.a., reveals four new
intermetallic compounds. Of these, Li,Ga, LiGa,, and LiGa, are identified by
X-ray d i f f r a ~ t i o n .The
~ ~ crystal structure of Li,Ge, formed in the Li-Ge
system has been determined by X-ray diffraction. The compound crystallizes
with the orthorhombic space group Cmmm, having a = 9.24, b = 13.21,
c = 4.63 A, d(expt) = 2.25, d(ca1c) = 2.28 for 2 = 4. Li,Ge, is not isostructural with Li,Si, but there are many similarities between the s t r u c t ~ r e s . ~ ~
For a series of molten Li-Sn alloys, direct measurements of e.m.f. from the
electrolytic cell (-) LilLiC1, LiFILi, Sn (+), carried out at 550 'C, indicate
substantial negative deviation from ideal beha~iour.~'
Phase equilibria in the
ternary system Wa-K-Rb have been investigated by thermal methods. The
ternary eutectic is at -18 "C, which is 5.7 "C lower than the Na-K binary
eutectic temperat~re.'~
The gaseous equilibria
NaAg(g) = W g )
and
NaAg(g)
+ Ag(g) = Na<@+
have been determined by using a double-oven technique in combination with

mass spectrometric analysis of the composition of the vapour. The Third Law
enthalpies AH: for these reactions are 32.0 f 0.3 and -65 f 0.2 kcal mol-l,
respectively. From these enthalpies the dissociation energy Dg(NaAg) is
31.8 =t3.0 kcal mol-l. The corresponding 0gg8
is 32.4 f 3.0 kcal mol-l.
The standard enthalpy of formation AH;,298 of NaAg(g) is calculated as
61.4 f 3.4 kcal mol-l. The experimental dissociation energy of NaAg(g)
is considerably lower than the value of 51 kcal mol-l calculated using the
Pauling model of a polar bond.79In an investigation of Na-Cd alloys from
20 to 86 atom % Cd by d.t.a., single-crystal and polycrystalline forms of the
compounds Na,Cd,, and NaCd, have been prepared. NaCd, is cubic,
a = 8.04 A, d(expt) = 5.7. Na,Cd,, is also cubic, a = 9.322 A, d(expt) = 7.1.
At 20% Cd, prismatic crystals are obtained which probably contain less Cd
than NaCd,.80 The phase diagram of Na-Hg has been re-investigated, and
changes in enthalpy, free energy, and entropy at 648 K are presented. As is
74
75
76
77
79
8o
K. Kuriyama, M. Yahagi, and KIwamura, Jap. J. Appl. Phys., 1973,12, 743.

S. P. Yatsenko, K. A. Chutonov, S. I. Alyamovskii, and E. N. Dieva, Izuest. Aknd.
Nauk S.S.S.R., Metal., 1973, 185.
V. Hopf, W. Mueller, and H. Schaefer, Z. Naturforsch., 1972, 27b, 1157.
A. 6.Morachevskii, L. N. Gerasimenko, A. I. Demidov, and 0. A. Drozdova,
Elektrokhimiya, 1972, 8, 1622.
B. J. Ott, J. R. Goates, and C. C. Hsu, J. Chem. Thermodynamics, 1973, 5 , 143.
V. Piacente and K. A. Gingerich, High Temp. Sci., 1972, 4, 312.
V. N. Kornienko and N. N. Zhuravlev, Kristallografiya, 1972, 17, 863.
12
Inorganic Chemistry of the Maingroup Elements

well known, the system forms a series of intermetallic compounds, amongst
which the congruently melting NaHg, is the most stable.*l
The velocity of sound in liquid metals and alloys, its variation with temperature, and its relation to the adiabatic and isothermal compressibility of the
metals has been reviewed. Experimental results are compared with theoretical
considerations.*2The velocity of sound at 7.5 MHz and the density have been
measured as functions of temperature for a number of solutions of metals in
liquid sodium. The results cover the whole concentration range for mercury
and the range 0-5 atom % solute for Au, Cd, In, Pb, and Sn. Changes in the
adiabatic compressibility and the mean molar volumes provide no convincing
evidence for compound formation in the Zipid phase of Na-Hg. There is,
however, a substantial volume contraction on mixing which apparently
causes the compressibility, when plotted against concentration, to fall well
below the straight line linking pure sodium with pure mercury. The contraction and the associated reduction in the adiabatic compressibility are not
peculiar to Na-Hg since the effects for all the different solutes used are
remarkably similar.83Evidence that compound formation does occur in the
liquid, however, comes from potentiometric measurements. The potentials
of homogeneous liquid sodium and potassium amalgams containing 0.657.19 (g atom Na)(l Hg)-l and 0.053-2.62 (g atom K)(l Hg)-l have been
measured at 25 and 50 "C. The experimental potentials, which are higher than
theoretical values calculated from the Turin-Nernst equation, are explained
by chemical interaction between Na (or K) with Hg. The number of atoms of
mercury co-ordinated with Na (or K) in liquid amalgams is calculated by the
Hildebrand equation, and, near saturation, is 5-6 and 15-16 for Na and K,
respe~tively.~~
Enthalpies of mixing sodium and gallium and the enthalpies of
formation of the two compounds NaGa, and Na,Ga, have been determined
calorimetrically at 723 K. Referred to the pure constituents in the liquid
state, the following values are found: AH, (NaGa,) 17.5 f 1.0, AH,(Na,Ga,)
-21.5 f 1.5 kJ mol-l. Using d.t.a., the latent heat of fusion of Na,Ga,
The density and surfxe tension of
was determined as 13.5 f 0.5 kJ m01-l.~~
five solutions of indium containing 0.5-7.0 atom% in liquid sodium have
been measured at 170-400 O C by means of the maximum-bubble-pressure
technique. The gram atomic volumes of these solutions, calculated from the
density, indicate a substantial contraction on mixing which is about twice
that for analogous Na-Cd solutions. The surface tension of liquid sodium
increases slightly on adding indium, indicating a lower concentration of
solute in the surface than in the bulk, in contrast to the marked surfaceactive behaviour of cadmium.86Two compounds are reported in the Na-Bi
A. Bykova and A. 6. Morachevskii, Zhur. priklad. Khim., 1973,46, 312.
G. M. B. Webber, Ultrason. Ind. Con$ Pap., 1970, 22.
83 S. P. MacAlister, Phil. Mag., 1972, 26, 853.
a 4 L. M. Ruban, A. I. Zebreva, and V. P. Gladyshev, Eiektrokhimiya, 1972, 8, 1021.
1 3 ~M. Gambino and J. P. Bros, Thermochimica Acta, 1973, 6, 129.
H. A. Davies, Met. Trans., 1972, 3, 2917.
a1 M.
Elements of Group I
13
system with very high melting points: Na,Bi, m.p. 775OC; NaBi (incongruently melting at 446 "C). These compounds are so stable that it is advantageous to consider them as independent components and to use for the liquid
alloys of this system a quasi-ideal-solution
Activities of potassium,
deduced from e.m.f. data, show that concentrations below 1 atom % in
liquid indium at 577 O C obey Henry's law, with a linear dependence of the
activity of K on its concentration in the alloy. The study also reveals a limited
solubility of potassium in indium.88Thermodynamic data on liquid alloys
of potassium with thallium over the complete concentration range have been
obtained from 350 to 550C using electrochemical cells of the type K(1)I
K-glasslK, Tl(1). Partial molar enthalpies and entropies of mixing are
calculated from the results. Some interesting maxima and minima are
observed which indicate a region of strong chemical interaction between
potassium and thallium.sgThe density of caesium vapour above solutions of
caesium in liquid rubidium has been determined from 293 to 313 K and mole
fraction Cs, x = 0.13-0.77. The density of the saturated vapour increases
with increasing caesium concentration. For a given concentration, the
density increases with increasing temperature. For all values of x at 5298 K,
and for x 2 0.35 at 2 3 1 3 K, the solutions showed negative deviations from
Raoult's law. If the solutions are sprayed on the vessel walls, effects due to
surface adsorption are observed.g0
4 Solvation of Alkali-metal Ions

Aqueous Solration.-A review, covering the 1968-1 972 publications, deals
with physical properties, thermodynamics, and structures of non-aqueous and
aqueous-non-aqueous solutions of electrolytes, and complete hydration
limits.g1 Thermodynamic aspects of ionic hydration also reviewed include
the thermodynamic theory of solvation; the molecular interpretation of ionic
hydration; hydration of gaseous ions (AG's, AH'S, and A S S ) ; thermodynamic properties of ions at infinite dilution in water, solvent isotope effect in
hydration; reference solvents ; and ionic hydration and excess proper tie^.^^
A third review on the hydration of ions emphasizes the structure of water in
the gaseous, liquid, and solid states; the size of ions; and the hydration
numbers of ions and the structure of the hydrated shell from measurements
of mobility, compressibility, activity, and from n.m.r. spectra.93Pure water
and aqueous LiCl at concentrations up to saturation have been examined by
neutron and X-ray diffraction. For the neutron studies 'LiCl and D20 are
employed. The data are consistent with a simple model involving only
A. G. Morachevskii, Elektrokhim. Rafnirovanie Tyazhelykh Legkoplavkikh Metal.
Rasplav. Solei, 1971, 37.
M. A. Bykova and A. G. Morachevskii, Izvest. V. U. Z., Tsuet. Met., 1973, 91.
89 S. Aronson and S. Lemont, J. Chem. Thermodynamics, 1973, 5, 155.
J. Ciurylo, Actu Phys. Polon. (A), 1973, 43, 737.
91 K. P. Mishchenko, 2hur.fiz. Kliim., 1972, 46, 2987.
9z H. L. Friedman and C. V. Krishnan, Water: Compr. Treatise 1973, 3 , 1.
93 H. Ohtaki, Kagaku (Kyoto), 1971,26, 1179.
87
14
Inorganic Chemistry of the Main-gvoup Elements

nearest-neighbour interactions. In the pure liquid and in dilute solutions the
structure of the water molecule resembles that in the vapour phase. Each
water molecule in the liquid is tetrahedrally co-ordinated by four others. This
basic water structure gradually diminishes with increasing LiCl concentration
and is not seen at mole ratios of ten or below. The co-ordination around Li+
appears to be tetrahedral, with co-ordination through oxygen. The C1- ions
are octahedrally co-ordinated through H.94A theoretical study concludes that
energetically the most favourable aquo-complexes of the ions Li+, Na+, and
K+ contain six, eight, and eight water molecules, respectively. The energy
E of [M(H,O),] t- complexes as a function of the distance between the metal
ion and the 0 atom is calculated according to the extended Huckel method,
assuming a donor-acceptor bond between H,O molecules and alkali-metal
ions. The bond energy of the aquo-complexes, AE, is obtained from AE =
E - n E ~ ~where
0 , E H ~isOthe energy of a free water molecule. The potentialinteratomic distance curves show a sharp minimum (AE,) for Li+ and Na+
ions but are shallow for K+. The values of AE,/n can be used as a measure
of the respective aquo-complex stability at higher temperatures. The flat
potential curve for K+ suggests both a larger contribution from the second
hydration shell to the total hydration shell and a greater mobility of water
molecules in the hydration layer of K+ than in that for Li+ and Na+.g5The
equilibrium constant K has been determined for the Li-isotope exchange
reaction :
7Li(s) %iCl(aq) = 6Li(s) LiCI(aq)
using an electrochemical quadruple cell without liquid junction. The value of

K at 296.6 K is 1.046 f 0.13 and, when compared with values of K calculated
from statistical thermodynamic theory for various model reactions, is
consistent with a tetrahedrally co-ordinated structure for the aquated lithium
Hydration numbers, however, when determined by acoustic-interferometer measurement of the adiabatic compressibility of the solution at
infinite dilution at 35 "C, have values Lif, 3 ; Rbf, 2; Ca2+,7, and Ba2+, 8.97
From literature data on the temperature dependence of the conductivity of
electrolytes, the radii rs of hydrated M+, M2+, and anions have been calculated using the equation Y, = O.82O/q,RO, where 7, is the viscosity/centipoise
Selected
and A, is the limiting equivalent conductance/cm2 equiv-l
values of r,/A at 25 O C are shown in Table 1, with crystal radii/A (Pauling)
Table 1 Valuesof rJA andPaulingcrysta1 radii rc/Afor ions in aqueous solution

Ion Li+ Na+ K+ Rb+ Cs+ NHf
rs
2.38 1.83 1.25 1.18 1.19 1.25
0.60 0.95 1.33 1.48 1.69 1.48
rc
O4
O5
O6
97
Mg2+ Ca2+ Ba2+ C1- Br- I1.54 1.44 1.20 1.17 1.0
1.73
0.65 0.99 1.35 1.81 1.95 2.16
A. H. Narten, E. Vaslow, and H. A. Levy, J. Chem. Phys., 1973, 58, 5017.

D. A. Zhogolev, Yu. A. Kruzlyak, B. Kh. Bunyatyan, and I. V. Matyash, Teor. i
eksp. Khim., 1972, 8,745.
G. Singh and P. A. Rock, J. Chem. Plzys., 1972, 57, 5556.
A. V. Satyavati, Current Sci., 1972, 41, 7334.
Elements of Group I
15
for comparison, With increasing temperature two phenomena affect hydration

numbers and hence radii; destruction of the free water structure, which leads
to higher hydration numbers since more water molecules become available,
and thermal motion, which acts in opposition. The decrease in Y, with increasing temperature is observed with Li+ and Mg2+ ions only. With larger ions
such as K+, Rbf, and Cs+ the negative hydration gradually changes to
positive hydration and Y, increases. In N-methylacetaniide, values for Y, of
Lif, Na+, and K+ ions decreased and those for R4N+ and halides increased
with increasing temperature. In structureless solvents such as nitrobenzene,
phenylacetonitrile, and dimethoxyethane, values of Y, of Nas and Css ions
are independent of temperature.9s The characteristic frequencies of water
molecules in hydration complexes have been investigated by neutron inelastic
scattering. For concentrated solutions of lithium and magnesium salts and of
calcium nitrate, the relaxation time of primary water of hydration increases
and exceeds interaction time. The self-diffusion coefficients for such complexes
decrease rapidly with decreasing temperature; with increasing anion basicity;
with both increasing mass of the cation and the number of water molecules in
its hydration sphere; and with increasing mass of anions and their bonding
to their primary water of hydration. In ternary solutions significant changes
occur in the bonding and ordering or water molecules in the hydrated spheres
of the component cations, in the diffusion kinetics of the water molecules,
and in the distribution of the anions relative to the cations.QgThe hydration
ability of concentrated hydrochloric acid (5.8 moll-l) is stronger than that of
lithium chloride. From the heats of mixing of these species with 1-6 moll-1
aqueous solutions of bivalent chlorides of Mg, Ca, and Sr it appears that
HCI removes more water molecules from the first co-ordination sphere of the
metal cation than LiCl. At lower salt concentrations the free water molecules
of the solution and not those bound to the inner co-ordination sphere of the
metal transfer to Li+ (or H+j.lo0 In the LiC10,-Ca(ClQ4j2-H,Q system at
25 "C, however, Ca2+ does not have a dehydrating effect on Lif since these
ions possess similar enthalpies of hydration in saturated aqueous solutions.lo1
The nuclear magnetic relaxation rates and shifts of 'Lit and 133Cs+in aqueous
solutions containing Fe3 I- and various counter-anions are interpreted in terms
of a dipolar attraction between Lis and the unpaired electrons on the Fe3+
ion, and the formation of an ion pair between Cs+ and ferric halide complex.lo2
An increase of pressure in the range 0-1000 bar results in an enhancement
in the hydration of the ions Naf and K+ in their aqueous chloride solutions.
The enhancement is more pronounced at 20 than at 45 "C. These conclusions
B. S . Krumgal'z, Zhur. srrukt. Khim., 1972, 13, 774.
G. I. Saford and P. S. Leung, US.Office Saline Water, Res. Develop. P r o p . Rept.,
1971, No. 708.
l o oZ. G . Szabo, M. Palfalvi-Rozsahegyi, and K. Burger, Proc. Symp. Co-ordination
Chern. 3rd, 1970, 1, 99.
lol S . A. Ivanov, Uch. Zap., Yaroslav. Gos. Pedagog. Inst., 1971, No. 95, p. 11. (Ref.
Zhur., Khim., 1972, Abstr. No. 7B907.)
lo2 M. Shporer, R. Poupko, a n d Z . Luz, Inorg. Chem., 1972, 11,2441.
O9
16
are drawn from an analysis of the literature data on the pressure dependence
of the adiabatic cornpre~sibility.~~~
Co-ordination of water molecules by
alkali-metal ions induces a distortion which shows up in the i.r. spectrum of
the molecule.l@This is more far-reaching, however, and the water structure
is destroyed by electrolytes in the order KI > K F > KBr > KCl; NaI >
NaBr > NaCl; LiI > LiBr > LiCl; LiCl > NaCl > KC1; LiBr > NaBr >
KBr; LiI > NaI > KI; KOH > NaOH > LiOH. Obviously the effect of any
cation on the structure of water depends greatly on its anion and vice versa.lo5
Calculations based on electrochemical data indicated that the primary
hydration number of caesium iodide is zero. Thus, the standard free energies
of transfer of Cs+ and I- from water to aqueous organic solvents should be
very low.lo6This is compatible with the order of extraction of alkali-metal
halides from aqueous solution byp-alkylphenols. Cs, Rb, and K are extracted
from chloride solutions at pH 9.5-13.8
by 0.5-4 mol 1-1 solutions of
alkylphenols (ROH; R = C, or C,) in kerosine by formation of ROM,nROH in the organic phase, n being 1.2, 1.2, and 2.2 for Cs, Rb, and K,
respectively. The distribution ratios between the organic and aqueous phases
from the aqueous solutions containing <0.15 mol 1-1 chlorides are D,, >
D,, > DK. On extraction, however, from solutions containing >0.15
mol 1-1 chlorides the sequence is reversed. The extraction from low metal
concentrations is governed mainly by the dehydration energy (low for
caesium) of the cations. In concentrated solutions, the dehydration energy of
the ions is levelled off to some extent, and the formation energy of the phenolate becomes the prominent factor influencing the extraction.lo7
As the dielectric constant of the solvent in which the alkali-metal ion is
dissolved decreases, then the degree of pairing with its counter-ion increases.
Thus the equivalent conductance of 2 x 10-4-1.5 x 10-2mol 1-1 lithium
chloride solutions in water-sulpholane mixtures (0-100 % water corresponding to a dielectric constant D from 43 to 75) at 35 OC, steadily decreases
as sulpholane is added, with noticeable ion-pair association for mixtures with
D < 62.1s Similarly with caesium bromide solutions.10g The diffusion
coefficients of the ions Cs+ and Br- in water-dioxan mixtures decrease with
increasing salt concentration. When interpreted on a model based on applicable ionic interaction theory, this is evidence for progressive ion-pair
formation. The vapour pressures above salt solutions (50.05moll-l) in
water-tetrahydrofuran mixtures are used to obtain the rate of change of the
ax,, with the solvent
standard chemical potential of the electrolytes, 3c0/
composition and to obtain solvation numbers. The compounds NaNO,,
Samoilov, A. L. Seifer, and N . A. Nevolina, Zltur. strukt. Khim., 1973, 14, 360.
I. Gudim, Dopooidi Akad. Nauk Ukrain. R.S.R., Ser. A , 1972, 34, 904.
l o 5 A. A. Ennan andV. A. Lapshin, Zhur. strukt. Khim., 1973,14,21.
Io6 T . Mussini and P. Longhi, Chimica e Industria, 1972, 54, 1093.
lo' Z . Abisheva, L. I. Pokrovskaya, A. M. Reznik, and V. E. Plyushchev, Izuest. Akad.
Nauk Kazakh. S.S.R., Ser. khim., 1972, 22, 2 8 .
lo*G. Petrella, M. Castagnolo, A. Sacco, and L. Lasalandra, Z . Naturforsch., 1972, 27a,
1349.
lo9H. Latrous, P. Turq, and M. Chemla, J. Chim. phys., 1972, 69, 1644.
lo30. Ya.
lo* L.
Elements of Group I
17
NaClO, are preferentially solvated by water ( @,/axl < 0) whereas NaCIO,

and NaBPh, are preferentially solvated by tetrahydrofuran (6'& axl > 0).l1O
In aqueous solutions containing sulpholane (1.01-95.33 %) at 25 'C, the
limiting equivalent conductances]cm2e q u i r l L2-l for KClO,, the association
constantslequiv 1-1 for ion pairing (K+ + ClO, = K+ClQT), and the ion-ion
contact distances/A in the solvated ion pair, respectively are 136.17, 0.69, 3.9
(1.01 %); 129.35, 0.60, 4.2 (5.62%); 70.14, 1.27, 4.6 (49.87%); 33.843, 5.23,
3.2 (80.78 %); 17.894, 18.25, 2.1 (95.33 % sulpholane).lll In aqueous 10.15 %
dioxan solutions at 25 O C , the preferential solvation of NaCl and NaOH by
water molecules and of NaBPH, and Ph,AsCl by dioxan molecules is indicated by changes in the standard chemical potentials (Ape) for transfer of the
electrolytes from pure water into the mixed solvent. The Apo values are
obtained from measurements, by gas-phase chromatography, of the composition of the vapour above the solutions. The selectivities (dpo]dx,; x1 =
mole fraction water) for dioxan solvation of the ions decrease in the order
BPh, > AsPhz >> Na+ > CI- > OH-, where Na+ is approximately equally
solvated by water and dioxan molecules. With decreasing xl,the differences
between the d,uo/dx, values decrease markeclly.l12 The limiting electrical
conductivities of 10-4-2 x 1W2 niol 1-1 LiCl solutions in 0-100 % waterDMF mixtures show minima near 25 % and 4 % DMF. These could be
attributed to either an exchange of the smaller water molecules for larger
DMF molecules in the solvent sheath of the ions, or a change in the solvent
structure, i.e. due to the appearance of DMF,3H,0.113 Sodium ion preferentially forms long-lived complexes with DMSO and DMF in mixtures of
either of these solvents with ethanenitrile or propanone. This is deduced from
the quadrupolar broadening of the 23Nan.m.r. in these solutions. In mixtures
of water or methanol with ethanenitrile or propanone, however, no longlived complexes are 0 b ~ e r v e d . l ~ ~
Some aqueous systems that have been investigated are listed in Table 2.115-160
Non-aqueous Solvation.-The absorption spectra of solutions of lithium and
of potassium in liquid ammonia at -7OOC have been measured using a
spectrophotometric cell incorporating sapphire windows. The envelope of
strongly overlapping bands in the 3200cm-l region of the pure solvent is
resolved into components which are assigned to 2v4, vl, and v, in increasing
energy. The N-H stretching frequency of the solvent shifts to lower energy
with increasing concentration of both lithium and potassium metal. Solvating
molecules have stretching vibrations of lower energy than bulk solvent
molecules. The solvated molecules, therefore, give an additional band
displaced from that for the solvent. The shift is independent of the nature of
the metal over the concentration range 5 x 10-,-5
x 10-2moll-1. This
112
113
114
C. Treiner, J. F. Bocquet, and M. Chemla, J. Chim. phys., 1973, 70, 472.

A. D'Aprano and I. D. Donato, Gazzeffa, 1972, 102,923.
S. Villermaux, V. Baudot, and J. J. Delpuech, Bull. SOC.chim. France, 1972, 1781.
Z . Kozlowski, Acta Chim. Acad. Sci. Hung., 1972, 17,49.
R. D. Green and J. S. Martin, Canad. J. Chem., 1972, 50, 3935.
Table 2 Aqueous systems that have been investigated

Components
LiB02-CO (NH 2)2

LiCNS-CO(NH2),
LiN03-CO(NH2),
Li2S04-K2S04-Rb,S04
LiCl-CsCl
LiI03-HI03
NaHC0,-Na3As04
Na2Si03-Na,P30,
NaN0,-NaNO,
NaN0,-NaCIO,
NaOH-Cd12
NaOH-A1 (OH),-K2S04
Na,SO,-MgS0,-CaSO,
Na,S04-CdS04
Na,S0,-Me2C0
Na CI-Na2S0,-Na2S O3
NaCI-AlC1,-E
t,O
NaC1-KC1-MgCIz-CaC1,
NaC1-NaC10,-NaC10,
NaCI-CsNO,
Na, (edta)-Al,( S04)3
KBOa-CO(NH2)2
KN03-NaNO,
Compounds
Ref.
2LiB02,CO(NH2)2,4H20
LiCNS,2CO(NH2)2; LiCNS,CO(NH,),
115
116
117
118
;
Li,S0,,K2S04 ; Li2S04,Rb2S0,
3Li,SQ4,Rb2S04,2H20
;
SLi2SO4,Rb2SO4,4H20
;
5LizS04;K2S04,Rb2SO4,2H20.
7NaHC03,Na3As04
4Na2S0,,3 CdSO, ,3Hz0
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137, 138
V. G. Skvortsov, Zhur. neorg. Khim., 1973, 18, 243.

R. Turgunbekova, K. Nogoev, and K. Sulaimankulov, Zhur. neorg. Khim., 1973, 18,
1 1 19.
117 K.-Abykeev, A. G. Bergman, and K. Sulaimankulov, Zhur. neorg. Khim., 1973,18,246.
118 I . N . Lepeshkov and I. M. Karataeva, Zhur. neorg. Khim., 1972, 17, 3341.
119 R. Vilcu and F. Irinei, Bull. SOC.chim. belges, 1972, 81, 479.
1 2 0 L. A. Azarova, E. E. Vinogradov, E. M. Mikhailova, and V. I. Pakhomov, Zhur.
neorg. Khim., 1973,18, 239.
i a i A. Akbaev, Zhur. priklad. Khim., 1973, 46, 648.
1 1 2 M. G. Manvelyan, V. D. Galstyan, E. A. Sayamyan, and A. G. Alakhanyan, Armyan.
khim. Zhur., 1972,25,840.
1 2 3 Ya. S. Shenkin, S. A. Ruchnova, and N. A. Rodionova, Zhur. neorg. Khim., 1973,
18, 235.
1 2 4 N. P. Andronova, Uch. Zap., Yaroslau. Gos. Pedagog. Inst., 1971, No. 95, p. 142.
(Ref. Zhur., Khim., 1972, Abstr. No. 7B905.)
1 2 5 E, A. Gyunner and I. G. Poltavtseva, Zhur. neorg. Khim., 1972, 17,2354.
1 2 6 P. F. Rza-Zade and M. A. Abbasov, Zssled. 061. Neorg. Fiz. Khim., 1971, 143. (Ref.
Zhur., Khim., 1972, Abstr. No. 22B813.)
127 I. E. Bytyrchaev and 0. Ryspaev, Zzuest. Akad. Nauk Kirg. S.S.R., 1972, 59.
128 A. S. Karnaukhov, T. P. Fedorenko, and V. G. Shevchuk, Uch. Zap., Yaroslau. Gos.
Pedagog. Znst., 1971, No. 95, p. 123. (Ref.Zhur., Khim., 1972, Abstr. No. 9B865.)
1 2 9 A. V. Krizhanovskii, E. S. Nenno, and R. M. Skripnichenko, Zhur. neorg. Khim.,
1972,17,2526.
130 M . A. Durymanova and A. E. Telepneva, Zhur. priklad. Khim., 1972,45, 1610.
131 V . I. Mikheeva. S. M. Arkhipov, and A. E. Pruntsev, Izuest. Akad. Nauk S.S.R., Ser.
khim., 1973, 1181.
132 M . Motoyama, M. Kadota, and S. Oka, Nippon Kaisui Gakkai-Shi, 1972,26, 16.
133 G. I<. Loseva, Tr. Nouocherkassk, Politekh. Inst., 1972, No. 266, p. 78. (Ref. Zhur.,
Khim., 1972, Abstr. N o . 15SS50.)
134 S. M. .4rkhipov, N. I. Kashina, and I. F. Poletaev, Zhur. priklad. Khim., 1973, 46,
985.
135 K. S. Merkulova, E. S. Bruile, and N. S. Dombrovskaya, Zhur. priklad. Khim., 1972,
45,2232.
136 V. G. Skvortsov, Zhur. priklad. Khim., 1972, 45, 2735.
137 A. M. Babenko, Zhur. neorg. Khim., 1972,17, 3059.
13I A. G. Bergman and L. F. Shulyak, Zhur. neorg. Khim., 1973, 18, 1379.
116
116
Table 2 Aqueous systems that have been investigated
(contd.)
Compounds
Components
Ref.
KNOB-CO (NH,),-Cr( N03)3 KNOs,CO(NH2), ;Cr (N03)B,6CO(NHz)21 39

140
K HaP04--NH4H,P04
K20-B203
K2OY5B203,8H20;K20,2B,03,4H20;
141
K2~B203~2H20
K,SO,-CsNH,
K,SO,-CsNH,-MnSO,
K,S04-(NH4)PS04-ZnS04
K,SO4-CdSO,
K,SO,-K,SO3
K,S,O,-KOH
KF-V205
KCl-KBr
KCI-MgCIz-K,SO,-Mg,SO,
KCI-NaCl-BaCI,
KCl-CaCl,
KC1-KNOB
KBr-NH,Br
KI-BI3-HI
KI-AgI
Rb,S0,-Al,(S04)B-MnS0,
RbCI-HaB03
Rb, Cr0,-CO (NH2)a
CS,S~~-(NH~)~SO~
CsI-CsBr
(NH4)zS04,ZnS84,6H20;
K,SO,,ZnSO, ,6H20
3CdSQ4,8H20 ;K2S0,,3CdS04,5M20;
2KzS04,2CdS04,3HzO
3KFYVz05
KCIYMgC1,,6H~0
;K2S04,2MgSO,
2KI,B13 ; KI,B13
KI,2AgI,2H20
RbsS04,A12(S04)3,24H20;
A12(S04)s,MnS04,22H20
;
A12(S04)3,5MnS04,23H20
;
Rb2S0,,MnS0,,6H,0
142
143
144
145
146
147
148
149
150
151
152
152
153
154
155
156
157
158
159
160
V. A. Tatarinov, Uch. Zap., Yaroslav. Gos. Pedagog. Inst., 1971, No. 95, p. 52. (Ref.
Zhur., Khim., 1972, Abstr. No. 7B926).
140 Ya. S. Shenkin, S. A. Ruchnova, and N. A. Rodionova, Zhur. neorg. Khim., 1972,17,
3368.
A. P. Solovev, Uch. Zap., Mord. Univ., 1971, No. 81, p. 39. (Ref. Zhur., Khim., 1972
Abstr. No. 12B799.)
142 A. K. Molodkin and 0. V. Geroleva, Zhur. neorg. Khim., 1972,17, 3379.
143 N. N. Runov, Uch. Zap., Yaroslav. Gos. Pedagog. Inst., 1971, No. 95, p. 72. (Ref.
Zhur., Khim., 1972, Abstr. N o . 7B939.)
144 V. N. Pilipchenko, L. Zharnovskaya, P. I. Trendovatskii, and V. M. Shpikula, Zhur.
neorg. Khim., 1972, 17, 3361.
lP6 V. K. Filippov, V. M. Makarevskii, and M. A. Yakimov, Zhur. neorg. Khim., 1973,
18, 1682.
146 V. K. Bishimbaev, I. N. Shokin, and A. G. Kuznetsova, Khim. Khim. Tekhnol.,
(Alma-Afa),1971, No. 12, p. 203. (Ref. Zhur., Khim., 1972, Abstr. No. 18B766.)
14 J. Balej. Coll. Czech. Chem. Comm., 1972, 37, 3855.
148 A. K. Sengupta and B. B. Bhaumik, Indian J. Chem., 1972, 10, 752.
149 K. G. Myakishev and A. P. Kostin, Zhur. neorg. Khim., 1973, 18, 271.
160 Yu. M. Timoshenko, Zhur. neorg. Khim., 1973, 18, 854.
151 T. V. Mozharova, V. A. Borovaya, and E. N. Pavlyuchenko, Zhur. priklad. Khim.,
1972,45, 1872.
lSzV. I. Vereshchagina, V. N. Derkacheva, L. F. Shulyak, and L. V. Zolotareva, Zhur.
neorg. Khim., 1973, 18, 507.
163 M. Nagatani and R. Kubo, Kagoshima Daigaku Kogakubu Kenkyu Hokoku, 1972,79.
L. V . Saveleva, S. B. Stepina, V. E. Plyushchev, and A. P. Rysev, Izoest. V. U.Z.,
Khim. i khim. Tekhnol., 1972,15, 1605.
155 N. Nishimura, T. Higashiyama, S. Yamamoto, and S. Hasegawa, Nippon Kagaku
Kaishi, 1973, 1059.
156 A. A. Maksimenko and V. Shevchuk, Zhur. neorg. Khim., 1973,18, 1401.
15 G. Gode and L. Klavina, Zhur. neorg. Khim., 1972, 17, 2851.
15* G . N. Zavorueva, Uch. Zap., Yaroslav. Gos. Pedagog. Inst., 1971, No. 95, p. 64.
159 Yu. V. Ushakov, Zhur. neorg. Khim., 1973, 18, 273.
160 Yu. G . Vlasov, B. L. Seleznev, and E. A. Elchin, Zhur. neorg. Khim., 1972, 17, 3069.
138
20
contrasts with the cation dependence of this band in solutions of salts in

ammonia, where the absorption is attributed to Mf - - - NH, dipole interactions. Also the magnitude of the v3 shift as a function of concentration is
greater for M than for Mf (400 times greater for K than for KI). These
results are attributed to the formation, with increasing metal concentration,
of a ncw solvated species of cation which incorporates the solvated electron,
i.e. a form of solvated cation-electron pair.161 The magnetic susceptibility of
solutions of alkali metals in liquid ammonia has been measured over the
concentration range where the solutions show a progressive transition towards
the metallic state. The general transport properties of metal-NH, solutions
have been analysed and a model is proposed for the mechanism of the transition to the metallic state.162This transition occurs at ca. 1-9 mole per cent
metal. Over this region metal-ammonia solutions exhibit rapid variations
with concentration of their static and transport properties. Concentrated
( > 10 mole per mole) metal-ammonia solutions are more like liquid metals
and show electronic transport. It is proposed that the intermediate 1-9
mol (mol)-l region is microscopically inhomogeneous, so that the solution
consists of a mixture of metallic clusters of a mean concentration >9 mol
(mol)-l together with small cation-electron diamagnetic c0mp1exes.l~~
Photoelectron emission by potassium (0.002-3 moll-l) and sodium (0.0130.21 and 7.2mol1-l) in liquid ammonia at -6OOC has been investigated
from 1.55 to 5.4 eV. The spectrum is composed of the previously reported
band at ca. 3.2 eV and a new band peaking at ca. 4.6 eV. The highly asymmetric low-energy band, 3.2 eV, is assigned to photoelectron emission by
solvated electrons. The 4.6 eV symmetrical photoelectron emission band
results from bound-bound transitions followed by a u t o i ~ n i z a t i o nAlkali
.~~~
metals dissolved in liquid ammonia react with zirconium disulphide ZrSz in
sealed tubes at 20C to form several phases. The alkali metals partially or
wholly occupy the layers of empty sites in the host structure to form NaZrS,
or KZrSz when the ammonia solutions contain high concentrations of
alkali metal. At lower concentrations, only one layer out of two is occupied.
No reduction of ZrS,, occurs. At very high concentrations, sodium occupies
octahedral sites whereas potassium occupies either octahedral or prismatic
sites. A comparison of the X-ray diffraction data of NaZrS, with those of ZrS,
indicates an increase in the lattice parameter c but little change in a upon
incorporation of sodium.165These compounds resemble those of TiS, with
the alkali metals. The compounds h4,TiS (M = Na or K) have been reported
previously. For M = Li, x = 0-1; M = Rb, x = 0.42-1, 0.12-0.32, and
0.04-0.06; M = Rb, x = 0.56-1, 0.08-0.10, and 0.03-0.04. The lattice
parameters of these compounds are compared with those of the sodium and
163
1G4
165
P. F. Rusch and J. J. Lagowski, J. Phys. Chern., 1973,77,210.

J. P. Lelieur, Report 1972, CEA-R-4333.
J. Jortner and M. H . Cohen, J. Chem. Phys., 1973, 58, 5170.
H. Aulich, B. Baron, P. Delahay, and R. Lugo, U.S. Nat. Tech. Inform. Service, AD
Rept. 1972, No. 750277.
J. Cousseau, L. Trichet, and J. Rouxel, Bull. SOC.chim. France, 1973, 872.
Elements of Group I
21
potassium phases, With increasing values of x in Li,TiS2, a and c increase

monotonically as the Li atoms progressively fill the octahedral sites of the
TiS2host lattice. The structures of the different types of phases are classified
on the basis of the co-ordination number of the intercalated alkali-metal
atom, the periodicity of the occupation of the available sites between
successive (STiS) layers of the host structure, and the mode of succession of
the sulphide layers.166Single crystals of MoS, can also be intercalated with
alkali metals (Li, Na, K, Rb, and Cs) by the liquid ammonia technique.
X-Ray results show considerable expansion of the c-axis after intercalation
(Ac; 6.745, 2.704, 4.286, 4.899, and 7.312 A for Li,.,MoS,, Na,.,MoS,,
KO,,MoS,, Rb,, ,MoS,, and Cs,. ,MoS2, respectively). All intercalated crystaIs
are superconducting, which is attributed to electron transfer from the alkali
metal to an empty band of M 0 S p 7 Potassium naphthalenide solutions also
react with MS, (M = Ti,Mo, or W) to give K,MS2 (x = 0.49-0.76). With
sodium naphthalenide, the first step in the reaction gives Na,MS,, but
lithium naphthalenide and subsequently sodium naphthalenide reduce the
sulphides to the respective metals.16*
The absorption spectra of solutions of alkali metals in various amines
display up to two bands; one at 1400 nm, which is independent of the metal
and which is attributed to a solvated electron, and a second band which peaks
between 660 and 1OOOnm which is independent of the metal and which is
attributed to a metal-containing species. Evidence has been accumulating
which suggests that this is a metal anion, M-, (J. P hp. Chem., 1971, 75,
3092). The 660-1000 nm band obeys the criterion for a charge-transfer-tosolvent transition that the position of the peak, Y , be a linear function of the
temperature coefficient, dv/dT. Thus the existence of the anion, M-, is
proposed in solutions of the alkali metals in MeNH, and EtNH,169and again
in solutions of Na and K in EtNH,, Et,NH, Pr,NH, propane-l,2-diamine,
(Me,N),PO, Et,O, PrizO, THF, MeOCH,CH,OMe, and diglyme, in which
the solubility of the metal has been enhanced by employing cyclic polyethers
of the crown and cryptate classes to complex the alkali-metal cations.170
For a spherically symmetrical Na species with J = 1 a magnetic moment of
1.0 B.M. is to be expected. Experimentally, values ranging from 0.5 to 1.3
B.M. are found for Na- in EtNH,.171
Modern advances in solvation theory are reviewed.17, A second critical
review of the thermodynamic functions and crystallographic data of some solid
solvates (e.g. NaI,3MeOH; LiC1,py; and CoC1,,6NH3) shows that the relative
acid-base properties of the constituent cation, anion, and solvate molecule
can well be described by the HSAB (hard and soft acids and bases) concept.173
lG6
lG7
lG8
lGS
170
171
172
173
J. Bichon, M. Danot, and J. Rouxel, Compt. rend., 1973, 276, C,1283.

R. B. Somoano, V. Hadek, and A. Rembaum, J . Chem. Phys., 1973, 58, 697.
E. Bayer and W . Ruedorff, Z. Naturforsch, 1972, 27b, 1336.
K. Bar-Eli and G. Gabor, J. Phys. Chem., 1973, 77, 323.
M. T. Lok, F. J. Tehan, and J. L. Dye, J. Phys. Chem., 1972, 76, 2975.
T. R. Tuttle, Chem. Phys. Letters, 1973, 20, 371.
H. L. Friedman, Chem. in Britain, 1973, 9 , 300.
C. Duboc, Ann. Chim. (France) 1973, 8 , 81.

The enthalpies of ammoniation of gaseous cations relative to that of Na+, and
of gaseous anions and the electron relative to that of I-, have been determined
from an analysis of enthalpies of solution of salts and metals in liquid
ammonia. Selected experimental enthalpies of formation, AH,/kcal m o F , of
ion pairs in liquid ammonia at -33 "C are shown in Table 3. The AHf of a
22
Table 3 Experimental values of AH,/kcal mol-l for ion pairs in liquid ammonia
at -33 "C
NO;
NHt
Li
Naf
K+
Rbf
Csf
Ca2+
Sr2+
Ba2+
-93.1
-126.1
-115.5
-117.4
-
-82.0
-75.2
-103.4
-96.4
-96.6
-93.4
-
-99.7
-
(-254.1)
I-
e-
-61.1
-82.9
-82.7
-84.2
(- 83)
- 190.6
-
-9.7
1.4
0
0
0
-19.7
-20.7
-19.0
Br-
C1-
certain ion pair, e.g. Na+ C1-, is found by combining the standard enthalpy of
formation of NaCl (-98.2 kcal mol-l) with its heat of solution in liquid
ammonia (-1.5 kcal mol-l). AH, of an ion-electron pair is merely the heat
of solution of the metal in liquid ammonia. Values in parenthesis are extrapolated. It is demonstrated that the relative ammoniation enthalpies of the
individual ions can be obtained from the Born equation if an effective radius
which is 0.61 13 greater than the crystalline radius is assumed for each ion. In
addition, the absolute ammoniation enthalpies for the gaseous ions are
evaluated at -33OC and compared with those deduced from the Born
equation. Values of AH/kcal mol-l for selected ions are shown in Table 4.174
Table 4 Experimental and calculated ammoniation enthalpies of some ions

Li+
K+
Ion
Expt.
Born
-133.3
-135.8
Na+
-105.4
-105.4
-83.9
-84.7
Ion
Expt.
Born
Sr2+
-370.2
-377.8
Ba2+
-335.7
-335.4
-86.3
-88.3
C1-
Rb+
-76.0
-78.6
Cs+
-70.3
-71.5
Ca2+
-402.7
-410.9
Br-84.3
-82.2
I-76.6
-74.4
e-36
-
Vibrational spectra, mostly from Raman scattering, are reported for LiNO,
and NH,NO, solutions in liquid ammonia ranging from dilute to the compositions LiNO,,l .6NH3 and NH,NO,,l .ONH, at ambient temperatures,
Large changes in the N-H stretching region are correlated with effects of the
electrolytes on the solvent structure. Low-frequency bands associated with
Li-NH, modes are observed. Some special features are indicative of both
114
N. M. Senozan, J. Inorg. Nuclear Chem., 1973, 35, 727.
Elements of Group I
23
solvent-separated and contact ion pairs involving Li+ and NO; ions.175The
enthalpies of solution at 25 OC for the salts LiCl, LiNO,, NaBr, Nal, NaNO,,
KBr, KI, KNO,, RbNO,, and CaNO, in DMF have been measured calorimetrically and the enthalpies of solvation of the component ions calc~1ated.l~~
Conductance measurements have been made at 25 "C for solutions of the
salts NaClO,, KClO,, LiNO,, NaNO,, KNO,, NaSCN, KSCN, NaBr,
potassium picrate, and Pr,NBr in hexamethylphosphortriamide (HMPT).
Potassium salts are more conducting than the corresponding sodium salts
and the ions migrate independently in HMPT. Alkali-metal cations are solvated by ca. 2HMPT moleculeswhereas the anions can be considered as naked.
All of the salts, except KNO, and Pr,NBr, are completely dissociated in this
s01vent.l~~
In solutions of perchlorates in hexamethylphosphoramide(HMPA),
the ionic equivalent conductivities of cations obtained on the assumption
that the conductivity of the perchlorate ion is 15.5 are Li+ 5.2, Na+ 5.8,
K+6.1, Rb+6.1, (36.4, Ca2+8.6, Sr2+8.6, Ba2+8.4, Me,N+7.9, Et,N+9.3,
Pr,N+ 6.8, Bu,N+ 5.9, and Hex,N+ 4.5 cm2 e q u i r l L2-l. The Stokes' Law
radius of a univalent cation is smallest for Et,N+. The solvation number
obtained from the effective ionic radius of Robinson and Stokes (1965) is
1 to 2 for alkali-metal ions and ca. 3 for alkaline-earth ions.178The association
of the ions Lif, Na+, and Mg2+ with perchlorate in methyl cyanide has been
studied spectroscopically. On increasing the salt concentration, additional
bands appear in the i.r. spectrum of the C 1 0 ions
~ owing to the formation of
M+Clog ion pairs: for solutions of Na+ these are at 1119, for Li+ at 1070
and 1132, and for Mg2+at 1040 and 1154 cm-1.179 The enthalpies of solution
of the salts LiClO, and LiNO, in isoamyl alcohol decrease with increasing
concentration, especially 50.1 moll-l. At 25 "C, the values at infinite
dilution are -9.90 kcal mol-l for LiClO, and -2.75 kcal mol-l for LiNO,.
The enthalpies of solution of the salts in the alcohol are more exothermic
than those in water,ls0A quantitative study of n.m.r. chemical-shift variation
as a function of salt (LiCl, LiBr, LiI, NaI, and KI), molality, and temperature
gives values for effective solvation numbers of 4 for lithium salts and 6 for
sodium and potassium iodides.lS1Conductivity data for solutions of sodium
iodide in acetone from -50 to +50 OC provide ionic association constants,
which with increasing temperature show a rise that is explained by the
endothermic effect of ion de-solvation. Positive values of entropy change
indicate that disorder increases during the ionic association of sodium
iodide.182The solvation numbers of Na+, K+, and I- ions at 25 "C, calculated
176
178
179
180
lE1
D. J. Gardiner, R. E. Hester, and W. E. L. Grossman, J. Chem. Phys., 1973,59, 175.

V. A. Zverev and G. A. Krestov, Teor. Rastuorov, 1971, 148. (Ref. Zhur., Khim., 1972,
Abstr. No. 6B1205.)
P. Bruno, M. R. Della Monica, and E. Righetti, J. Phys. Chem., 1973, 77, 1258.
T. Fujinaga, K. Izutsu, and S. Sakura, Nippon Kagaku Kaishi, 1973, 191.
I. S. Perelygin and M. A. Klimchuk, Ural. Konf. Spektrosk., 7th, 1971, No. 2, p. 125.
P. A. Skabichevskii and I. I. Klement'eva, Zhur.fiz. Khim., 1973, 47, 692.
A. Lindheimer and B. Brun. J . chim. Phys., 1972, 69, 1454.
B. S. Krumgal'z and Yu. I. Gerzhberg, Zhur. obshchei Khim., 1973, 43, 462.
24
from conductance data for solutions of NaI, KI, and KSCN in acetone,
when compared with solvation numbers for the same ions in ethanol and
water, illustrate that the intrinsic structure of the solvent plays a major role
in the solvation process.ls3 The i.r. spectra of solutions of Li, Na, K, Rb,
and Cs salts in sulpholane show absorptions which are independent of the
anion. Solvation appears to take place in a manner similar to that observed
for DMSO solutions but sulpholane, a dipolar solvent with a high (44)
dielectric constant, is a far weaker donor. It is proposed that solvent-separated
ion pairs are formed in sulpholane solutions.1s4The electrical conductivities
of solutions of the Li, Na, K, and Rb salts of 2,4-dinitrophenol in THF at
25 O C have been measured with and without added triphenylphosphine oxide.
Ion-pair dissociation constants of the salts are derived from variation of the
conductivities with salt concentration. These constants increase with increasing cation size, as expected for contact ion pairs. Cation-ligand association
constants, KL, are derived from the increases in the conductivities due to
added Ph,PO. Values for KL are for Li 3500, Na 250, K 87, and Rb 53 I mol-l.
This is just the order of association expected from the cationic radii. An iondipole model, modified to take into account the influence of surrounding
polarizable solvent, is able to explain the re~u1ts.l~~
Ion-solvent interactions
are detected in cyclohexane solutions of NaAlBu, by means of differential
vapour pressure analysis. The observed departure from ideality is attributed
to an aggregation process. The apparent degree of aggregation varies from
pairs of ions at ca. 0.0025 niol 1-1 to an aggregation number of 6 at ca.
2 moll-l. Addition of THF to the salt solutions lowers the apparent molecular
weight of the solute. The magnitude of this effect increases with both an
increase in the ratio of THF:NaAlBu, and with an increase in NaAlBu,
concentration. This is attributed to a loss of aggregate stability in both
instances.ls6 Thermochemical measurements on solutions of sodium iodide
and caesium iodide in DMSO at 25 "C provide integral enthalpies of solution.
With solutions of NaI, an increase in salt concentration causes an increase in
the exothermic effect attributed to the ability of NaI to form solvates with
Me,SQ. The energetics of solvation of Na+ ions are appreciably greater than
those for Cs+ ions.lS7In anhydrous acetic acid solutions containing 0.0010.032 mol 1-1 metal acetate at 25 O C , the dissociation constants ( K B ) for
M+OAc- = M+ OAc-, determined by a potentiometric method, are
PKB = 6.13 & 0.04, 5.93 f 0.10, and 5.84 f 0.10 for M = K, Rb, and Cs,
respectively. For M = Li, Na, K, Rb, and Cs the linear plot of pKB us. log a3
has a slope of +1, where a is the radius of M+.ls8 The optical absorption
spectra have been measured for solutions of triphenylene reduced with alkali
Yu. I. Gerzhberg, B. S. Krumgal'z, and D. G. Traber, Teor. Rastvoroo, 1971, 115

lE4 T. L. Buxton and J. A. Caruso, J. Phys. Chem., 1973, 77, 1882.
lS5 H. B. Flora and W. R. Gilkerson, J. Phys. Chem., 1973, 77, 1421.
lS6 J. H. Muller and M. C. Day, J . Phys. Chem., 1972, 76, 3472.
lS7 0. I. Kyabchenko, M. L. Klyueva, K. P. Mishchenko, and N. P. Novoselov, Zhur.
ohshchei Khim., 1973, 43, 467.
l g 8 0. W. Kolling and H. E. Gracey, Inorg. Chem., 1972, 11, 2556.
lS3
Elements of Group I
25
metals in 2-methyltetrahydrofuran from -155 to +75 'C. Several ion pairs

are observed; a linear correlation between v and reciprocal cation radius is
observed for both solvated and contact ion pairs. The low-temperature spectra
show a clear equilibrium between two types of ion pairs at high triphenylene anion concentrations. The high-temperature spectra show a gradual
increase in Y as the temperature is increased, which is interpreted on the
basis of an equilibrium between solvated and contact ion pairs.lE9
5 Compounds containing Organic Molecules or Complex Ions

Certain naturally occurring antibiotics show a high degree of cation specificity
for the alkali-metal ions in biological systems. Selectivity is in the order
Li+ << Naf, Csf <Rb+, K+. Significantly, this is the order of the magnitude
of the stability constants for their complexes with alkali-metal ions. Simulation of the selective behaviour in simpler systems than those of naturally
occurring antibiotics can be achieved with cyclic polyethers. The structures of
some polyether-alkali-metal salt complexes are already known. The first
compounds to be isolated have the stoicheiometry 1:1, i.e. one mole of
cyclic ether to one mole of metal salt. The stability constant is greatest when
the metal cation fits the centre of the ring of oxygen atoms in the organic
molecule. Given the optimum match between size of hole and size of cation,
K+ forms the strongest complexes. This can be explained on an ionic model;
the cation is not small enough for its hydration energy to be so large that
complexing with the cyclic polyether is precluded and, moreover, the cation
is not large enough to prevent strong ion-dipole interaction with the oxygenring in the polyether. Recently, a meta1:ligand ratio of 2: 1 has been found
in (KCNS),L,, and complexes of ratios 1 :2 and 2:3 have been obtained if the
cation is too large to fit the hole in the ring. The most recent study is on the
crystal structure of the 1 : 2 complex KI(benzo-15-crown), formed between KI
and 2,3,5,6,8,9,11,12-octahydro-l,4,7,10,13-benzopentaoxacyclo-pentadecin,
i.e. benzo-15-crown 5. The compound C,,H4,KI0,, is tetragonal; a , b =
17.84, c = 9.750 A, d(X-ray) 1.51 for 2 = 4, d(expt) = 1.51, space group
P4/n. Bond lengths/A are shown in (l), the standard deviations in the K-0
bonds being 0.007-0.008 A. K+ is sandwiched between two organic molecules
and is co-ordinated to ten oxygen atoms in an irregular pentagonal prism
as shown in Figure 1. The complex cations are separated by iodide ions in an
arrangement resembling that in CsCl. There is no interaction between K+
and I-.190 The equivalent conductance for NaCl, KCl, CsCl, NaBPh,,
KBPh,, and CsBPh, in methanol and acetonitrile solutions containing the
cyclic polyethers dibenzo-1%crown 6 and dicyclohexyl-1%crown 6 have been
measured at 10 and 25 "C and in salt concentrations up to 0.004 molld1. The
189
lS0
R. M. Arick, J. A. M. Van Broekhoven, F. W. Pijpers, and E. DeBoer, J . Amer. Chem.

SOC.,
1972,94, 7531.
P. R. Mallinson and M. R. Truter, J . C. S. Perkiiz ZZ, 1972, 1818.
26
A3
decrease in equivalent conductance caused by the addition of a cyclic polyether is analysed to give association constants and equivalent conductances
of the cation-polyether complexes. The selectivity observed for complexing
is a function not only of ionic size but also of solvent.1g1The stability constants
Figure 1 The complex cation of potassium with benzo-15-crown 5
of the cryptate-type co-ordination complexes of the macrobicyclic ligands

(2; R1 = R2 = H, X = 0 or CH,; R2R2= benzo, R1 = H, X = 0 ;RIR1=
R2R2 = benzo, X = 0) and the macrocycle (3) with Naf, Kf, and Ba2f
ions have been determined in 95 :5 MeOH-H20 mixtures and compared with
lS1
D. F. Evans, S . L. Wellington, J. A. Nadis, and E.L. Cussler, J. Solution Chem., 1972,

1,499.
27
Elements of Group I
MeN
NMe
those for nonactin. The stabilities of the cryptates are controlled by the thickness, s, of the organic ligand layer separating the complexed cation from the
solvent. Increasing S decreases the attraction of the complexed cation for the
polar solvent, e.g. H,O, and destabilizes the complex. Selectivity for Ba2+
Over K+ is introduced since, though of similar size, the attraction is stronger
for bivalent than univalent cations. The presence of fewer binding sites, i.e.
oxygen atoms, in the ligand also destabilizes the c0mplex.1~~
Potassium
cryptate, (Cl,H3,N,0,K)+I-, crystallizes in the monoclinic system with four
molecules in a unit cell of symmetry C2/c and dimensions a = 14.424,
b = 8.334, c = 20.638 A, P = 103.50'. The complex cation has D, symmetry
and is located at the centre of the molecular cavity of the bicyclic ligand,
surrounded by all eight heteroatoms of the ligand as shown in Figure 2.
N
Figure 2 Heteroatom cage round K+ in potassium iodide cryp tate,

(c1sH360 GNzK)+I-
The six oxygen atoms comprise a prism distorted towards an antiprism (the
torsion angle between the two triangular faces is 22'53'). The two nitrogen
atoms lie above and below, respectively, the centres of the two triangular
faces on a line through the central K atom. Using the given notation, the
K-N, K-Q(4), K--0(21), and K-0(7) distances are 2.874, 2.776, 2.790,
and 2.789A, respectively. The rest of the complex has been omitted for
its three adjacent oxygen
clarity but each N is linked through-(CH,),-to
atoms. Pairs of oxygen atoms in top and bottom triangular faces are similarly
B.Dietrich, J. M. Lehn, and J. P. Sauvage, J . C . S . Chem. Comm., 1973, 15.
lua
28
linked, e.g. o(7)-(CH2)2-o(4).

The K-I distances are all greater than
6.5A .lg3Analogous complex cations are found in rubidium and caesium
cryptates, C18H,,N206,MSCN,H20. This indicates the flexibility of the
organic bicyclic ligand, which adapts its molecular cavity to the ionic radius
of the metal. These isomorphous monoclinic compounds with space group
P2/c and four formula units per cell have dimensions a = 22.66, b = 8.31,
c = 14.41 A;
= 109.75" and a = 22.68, b = 8.33, c = 14.400 A, tfl =
109.03" for M = Rb and Cs,respectively.lg4In sodium cryptate,C18H,,N,0,,NaI, the structure of the complex cation is again similar to those of K, Rb,
and Cs, although the overall structure is hexagonal with a, b = 8.630,
c = 18.570& 7 = 120, and 2 = 4. The crystal is again made up of ionic
packing of (Cl,H3,N20,Na)+ cations and I- anions.lg5In ethylenediamine,
below the coalescence temperature of 50 OC, separate 23Nan.m.r. signals can
be obtained for the solvated Naf and for the Na+ ion complexed in a cryptate.
The doublet coalesces and the exchange narrows with increasing temperature.
The first-order rate constant for complex cation dissociation in ethylenediamine varies from 300s-l at 34OC to 2560s-I at 75 O C . An activation
energy of 12.2 f 1.1 kcal mol-l is found. The rate of dissociation is similar
to that found for aqueous solutions.196The final compound in this series,
lithium cryptate, C14H2,N204,LiI,is tetragonal with space group p4,2,2,,
with 2 = 4 and unit-cell dimensions a , b = 8.723, c = 24.361 A. The Li+
cation is again enclosed within the molecular cage but the co-ordinating
ligand in (4) contains two fewer 0 atoms than do the analogous complexes ( 5 )
(4) M = Na, K, Rb, or Cs
of the other alkali metals, Na, K, Rb, and Cs. The small Li+ ion occupies a
severely distorted octahedral environment comprising two nitrogen atoms at
2.288, two 0 at 2.173, and two 0 at 2.081 A distant from the central metal
ion.lS7The crystal structures of complexes of alkali-metal thiocyanates with
the antibiotic tetranactin have been determined. The biological property of
nonactins is to transport alkali-metal ions through biological membranes in
the form of complexes. The uncomplexed tetranactin molecule is fairly flat,
elongated, and twisted; the molecular outline resembles that of a propeller.
lS3
lS4
lg5
lg6
lS7
D. Moras, B. Metz, and R. Weiss, Acta Cryst., 1973, 293, 383.

D. Moras, B. Metz, and R. Weiss, Acta Cryst., 1973, 29B, 388.
D. Moras and R. Weiss, Acta Cryst., 1973, 29B, 396.
J. M.Ceraso and J. L. Dye, J. Amer. Chem. SOC.,1973, 95,4432.
D. Moras and R. Weiss, Acta Cryst., 1973, 29B, 400.
Elements of Group I
29
On complexing with alkali-metal ions the molecule curls up to enclose the

cation in an eight-membered distorted cube of oxygen atoms (labelled 4, 54,
12, 62, 17,67,22, and 72, according with the original article) as shown in (6).
The complex compounds are all monoclinic, with the properties shown in
Table 5.1g8
Table 5 Properties of complexes of tetranactin with alkali-metal ions
Coiilplex
Form
Space group
alA
blA
CIA
Mean M+- - -0< distances/A

(4) (541, ( 12) (62)
Mean M+- - -8= distanceslA
(17)(67), (22)(72)
Na
C2/c
I
C2/c
Rb
I1
P2Jn
27.484
12.364
30.050
97'18'
2.820
27.455
12.420
30.21~
2.874
15.796
20.630
15.613
90'18'
2.893
2.435
2.774
2.789
98'09'
P2Jn
15.972
20.555
15.495
9023'
2.940
2.909
Other complexes involving thiocyanate are those of LiSCN with 1,5,9,13tetraoxacyclohexadecane and its 3,3,7,7,11,11,15,15-octamethylderivative.
These organic molecules form stable complexes with 2 moles of LiSCN or
1 mole of LiBr or LiI, as shown by changes in the lH n.m.r. spectrum of the
ligand.lgQThe cyclic quadridentate secondary amine 1,4,8,1l-tetra-azacyclotetradecane (cyclam) also reacts with lithiumsalts to give complexesof the type
(LiX),(cyclam) when X = Br, I, or ClO,. A 1 :1 complex is also produced
with LiClO,. The i.r. spectra of the 2: 1 complexes are similar to each other
but differ from that of free cyclam. (LiClO,),(cyclam) and LiI(cyc1am) are
triclinic, with Z = 1. LiClQ,(cyclam) is body-centred tetragonal with 2 = 2 ,
so that the N atoms are crystallographically equivalent and probably tetrahedrally co-ordinated to Li+.,O0 The interaction of sucrose with alkali-metal
l9*
Ig9
Y . Iitaka, T. Sakamaki, and Y . Nawata, Chem. Letters, 1972, 1225.

J. Dale and J. Krane, J . C . S . Chem. Comm., 1972, 1012.
D. E. Fenton, C . Nave, and M. R. Truter, J. C . S. Chem. Comm., 1972, 1303.
30

halides MX has been studied potentiometrically. Complexes form which
correspond to the general formula (MX),L,, where L = sucrose, n = 4-1,
and rn = 1-3. The complexing ability of the cations decreases in the order
Na+ > Li+ > K+.201The 1 : 1 complex of bis-(4-aminophenyl)methane with
NaCl has been prepared. The spectrum shows important differences between
the complex and the free ligand at 650 and 1200 cm-l. X-Ray data show octahedral geometry round both Na+ and C1-ions.202The following addition compounds of thiourea (tu) with perchlorates have been prepared: LiC104,3.5tu;
NaClO, ,3.5tu ; Be(ClO,), ,6tu ; Mg(C10,),,6 tu ; Ca(C10,)2,7-8tu ;Ba(ClO,), ,
8-10t~.~O~
The crystal structure of the complex triphenylmethyl-lithium tetramethylenediamine, Ph3C- Li+ Me2N(CH,),NMe2, has been determined from
X-ray data. The compound is monoclinic, space group P2,/c, with a = 8.546,
b = 16.171, c = 16.999 A, = 106.75', 2 = 2 , d(obs) = 1.0, d(ca1c) = 1.07.
The structure can be described as a contact ion pair consisting of a lithium
cation co-ordinated to a tmeda group and a triphenylmethyl carbanion (7).
Each Li atom is co-ordinated to two N atoms of the bidentate chelate and to

one ?r-carbanion. Each Li-N distance is 2.10 A. The Li atom is not located
directly over any one carbon atom but has four close contacts to the carbanion; 2.49 and 2.51 A to two C atoms on one phenyl group, one close
contact of 2.54A to one C atom of a second phenyl group, and one 2.23 A
distance to the central carbon atom. The twist angles of the phenyl rings
depend on their interaction with the Li atom, giving an overall propeller
geometry to the triphenylmethyl carbanion. It is not possible to explain the
stereochemistry by two-centre 0 or ionic interactions alone, and a delocalized
bonding mechanism which involves all the 2s and 2p orbitals of the Li
201 A. J. Dangre, J . Univ. Poona, Sci. Techiiol., 1972, No. 42, p. 131.
ma F. Klema, Mitt. Chem. Forschungsinst. Wirt. Oesterr. Oesterr. Kunststojinst., 1972,26,
101.
Io3 N. Pustelnik and R. Soloniewiez, Roczniki Chem., 1972, 46, 1961.
Elements of Group I
31
atom is inv0ked.2~~
There are distinct similarities between this compound
and [K(MeOCH2CH2),0][Ce(C&)2]. The structure of the latter consists of
an ether-co-ordinated potassium cation [K(MeOCH,CH,)20]f combined in a
contact ion pair with a discrete [Ce(C,H,)]- anion (8). One side of the cation
is co-ordinated by the complexing ether diglyme, which has normal bond

distances and angles. The opposite side is co-ordinated by one of the two
cyclo-octatetraenyl dianion rings in the structure. The potassium lies on the
crystallographic mirror plane. The two independent K-0 distances from the
0 atoms in the ether are 2.792 and 2.741 A and the five independent K-C
distances between the K+ ion and the C,H;- ring average 3.16 A. The salt
crystallizes from diglyme as large green plates for which the crystal data are
orthorhombic, space group Pnma, a = 16.897, b = 14.014, c = 9.358 A,
d(obs) = 1.330, d(ca1c) = 1.324 for 2 = 4.205The isomorphous adducts
[M(~alen)~],
NaBPh4,2THF [M = Co, Ni, or Cu; salen = NN'-ethylenebis(salicylideneiminato)] have been prepared from the components in THF.
Crystals of the cobalt compound are monoclinic, space group P2,/c, with
a = 14.415, b = 14.329, c = 27.897 A, = 98.0,d(obs) = 1.330,d(calc) =
1.324 for 2 = 4. The crystals consist of discrete [Co2(salen),,Na,2THF]+
cations and [BPhJ anions. The anions, held together by phenyl-phenyl
interactions, are arranged in planes with the complex cation between, as
shown in Figure 3. The sodium atom has approximate octahedral co-ordination, being surrounded by six 0 atoms, two from each Co(sa1en) group
(Na-0 distances ranging from 2.391 to 2.482 A) and one from each of the
two THF groups (Na-0 distances 2.35 and 2.37 A) in the complex cation,
which has approximately C2symmetry. This is an example of an alkali-metal
ion complexed to a co-ordination compound. The following adducts are
204
a05
J. J. Brooks, W. Rhine, and G . D. Stucky, J . Amer. Chem. SOC.,1972, 94, 7346.

K. 0. Hodgson and K. N. Raymond, Inorg. Chem., 1972,11, 3030.
32
eo
ON
oc
Qhb
Figure 3 View of the [Co,(salen),Na,(THF),]+ cation, with some relevant

bond distances.
similarly prepared: [3MeOCo(salen)],,NaBPh4,2THF; M(salen),LiX,THF
(M = Co, X = Br, I, or SCN; M = Cu, X = SCN); 3-MeOCo(salen),LiBr,THF; and ~-M~O.CO(S~I~~),L~SCN,TKF.~~
The crystal structure of rubidium ammonium hydrogen fluorocitrate dihydrate Rb(NH4)H(C*H40,F),2H,O has been determined. The crystals are triclinic, of space group PI, 2 =
2, with a = 8.458, b = 10.910, c = 7.516 A, a = 102.80", /3 = 115.90,
y = 80.50,d(ca1c) = 1.925, d(obs) = 1.92. The co-ordination of rubidium is
unusual in this type of compound owing to the presence of the fluorine atom,
as shown in (9). The fluorocitrate ion forms a terdentate chelate with the
metal through F , through the 0 of the carboxylic acid group adjacent to F,

and through the 0 of the hydroxy-group. The central carboxy-group is not
involved in this chelation, contrary to the case for citrates and isocitrates.
The fluorine, by virtue of its electronegativity, in no way resembles an H
atom but is chelated to the metal. Overall there are six 0 and two F atoms
round any Rb+ ion but only five 0 atoms round the NH$ cation; F is always
206
C. Floriani, F. Calderazzo, and L. Randaccio, J. C. S. Chem. Comm., 1973, 384.
Elements of Group I
33
co-ordinated to Rb+ rather than to N H i in this structure.207The crystal

structure of a rubidium salt of homophthalic acid, o-HO,CC,H,CH,CO,H
(H,A), has been determined with the formula Rb(C,H,.508)2, i.e.RbHA,H,A.
The compound is monoclinic, space group C2/c, a = 32.81, b = 5.47,
c = 9.95 A,?! , = 95"54', 2 = 8. The rubidium ion is tetrahedrally (distorted)
co-ordinated by four oxygen atoms at distances 2.86 and 2.88 A. Each 0
belongs to a different homophthalic acid molecule. The two acid molecules
linked with one Rb+ ion form a chelate complex which is repeated throughout
the structure. Linking between the acid molecules is achieved by short
(2.61 A) and ultra-short (2.45 A) hydrogen-bonds between oxygen atoms of
carboxy-groups.208In potassium boromalate monohydrate KBC8H8O1o,H@,
the alkali-metal ion is again co-ordinated by the oxygen atoms of the carboxygroups but in this case K+ exhibits five-co-ordination209The thermal decomposition of alkali-metal halogenoacetates has been studied by gas
chromatography, d.t.a., and thermogravimetric, X-ray, and chemical
analyses. The decomposition of the salts (M = Li, Na, K , or NH,) proceeds
according to CH,ClCO,M
H,O
CO C
MCl and 2CH2C1CO,M -+
2H,O
CO, 3C 2MC1 at low and rapid heating rates,respectively.2101n
the phase equilibria between alkali-metal chloroacetates (MA)-CH,ClCO,H
(HA)-H,O at 20 "C, the existence of 2LiA,HA is proven in the lithium system
but attempts to prepare it in the pure form failed. In the corresponding
sodium system, only NaA and HA are present. The potassium system contains KA,HA and this compound is the most insoluble. Two compounds exist
in the rubidium system, RbA,HA and RbA,2HA. Similarly, in the caesium
system there exist CsA,HA and 3CsA,SHA, of which the first compound is
very stable. The behaviour of the ammonium system resembles that of potassium. The ability to form complex compounds increases with increasing radius
of the cation.211 The lithium, potassium, and ammonium monochloroacetates, when dissolved in D M F at 20 "C, show conductivities characteristic of
weak or medium-strength acids. The structures of the compounds are given.212
In the mixed fluoro(trifluoroacetato)iodate(iII) series Cs,IF,,(O,CCF,),-,,,
where n = 0-3, the still missing Cs,IF,(O,CCF,), and Cs,TF,(O,CCF,), have
been prepared by the reaction of Cs,IF6 with (CF,CO),O in CCl,F at -40 "C,
and CsI(O,CCF,), with CsF in CC1,F at 20 'C,respectively. Potassium iodate
reacts similarly with (CF,CO),O in acetonitrile to give the compound
KIO,(O,CCF,),. In the analogous reaction of KBrO,, an explosion occurred
accompanied by evolution of Br,, CO,, and C,F,.,13 The i.r. reflection
(20-3600 cm-l) and Raman scattering polarized spectra of isotopic single
207
208
209
211
212
213
+ +
H. L. Carrel1 and J. P. Glusker, Acta Cryst., 1973, 29B, 674.

M. P. Gupta and D. S. Dubey, Z . Kristallogr. Kristallgeom. Kristallphys., Kristallchem.,
1972, 135, 273.
R. A. Mariezcurrena and S. E. Rasmussen, Acta Cryst., 1973, 29B, 1035.
J. Pokorny, Sb. Vys. Sk. Chem-Technol. Praze. Anorg. Chem. Technol., 1972, B14, 153.
J. Pokorny, Sb. Vys. Sk. CJiem-Technol. Praze, Anorg. Chem. Technol., 1972, B14, 167.
J. Pokorny, Sb. Vys. Sk. Chem-Technol. Praze, Aizorg. Chem. Technol., 1972, B14, 175.
D. Naumann, H. Dolliaine, and W. Stopschinski, 2. anorg. Chem., 1972, 394, 133.
Inorganic Chemistry of the Main-groupElements
34
crystals of lithium acetate, 'Li0Ac,2H2O, 6LiOAc,2H20,and 'LiOAc,2D20,

confirm the structure previously determined.214Crystal data for potassium,
rubidium, and caesium acetates have been determined. Potassium acetate
undergoes two phase transitions, at 75 and 155 "C. The sequence of phases is
monoclinic, monoclinic with an eight-fold decrease in cell volume, and
orthorhombic. The orthorhombic phase is stable up to the m.p.216 The heats
of fusion of the acetates of sodium, potassium, rubidium, and caesium as
determined by d.t.a. are 4.2, 5.4, 3.5, and 2.3 kcal mol-l, respectively.216
Potassium thioacetate KCH,COS is orthorhombic, with a = 9.702, b =
4.212, c = 11.756 A, d(expt) = 1.58, d(ca1c) = 1.57 for 2 = 4, space group
Pnma or Pn21a.217 Potassium oxalate K2C204,H20thermally decomposes
with dehydration below 100 "C, followed by decomposition of K2C204at
450-600 "C to K,CO, and CO. A well-defined phase transition in K2C204
is observed at 390C by d.t.a. Five steps are seen in the decomposition of
KHC204,H2C204
,2H20, producing successively the solids KHCz04,H2C204,
then KCH,04, followed by K2C2O4, and K,CO,. In the decomposition of
KHC204the first step is explosive, to give K2C204, which breaks down as
described above for K,C20,,H_20.21s
Crystals of lithium succinate(CH2C0,Li),
are trigonal, space group R3, with hexagonal cell parameters a = 12.026,
c = 10.625 A, a n d Z = 9. The succinate ion has a centre of symmetry between
the central C atoms. Four 0 atoms form a slightly deformed tetrahedron
around the lithium ion, with Li-0 distances ranging between 1.943 and
1.961 A?19
6 Alkali-metal Oxides
Molecular species in the lithium-oxygen system have been studied by electronimpact mass spectrometry. From a study of the gaseous equilibria:
+ 0,= LiO + 0
Li,O + 0 = 2LiO
Li
and
and from the composition of the saturated vapour over Li20 (condensed),
the dissociation energy Do0 of the LiO species is 80.5 f 1.5 kcal mol-l.
Previously reported values are 76.9 f 5, 77 f 6, and 81.4 f 3 kcal mol-l.
The derived enthalpy of formation AH& for LiO is 16.5 f 1.5 kcal mol-l,
based mainly on the present measurements. The ionization potentials are
I.P.(LiO) 8.45 eV and I.P.(Li,O) 6.19 eV, with an uncertainty of 0.20 eV,
giving AhHf"(Li0f)211.5 kcal mol-l and AH;(Li,O+) 103.1 kcal mol-l. The
binding energies D:(Li+-OLi), D:(Li+-O)
are calculated as 3.28 k 0.22 eV
214
M. Cadene and A. M. Vergnoux, Spectrochim. Acta, 1972, 28A, 1663.
215
J. Hatibarau and G. S. Parry, Acta Cryst., 1972, 28B, 3099.

S. S. Potemin, A. A. Tarasov, and 0. B. Panin, Vestnik Leningrad. Univ. (Fiz. Khim.),
216
217
218
219
1973, 86.
M. M. Bore1 and M. Ledesert. Compt. rend., 1973, 276, C 181.
A. H. Verdonk, Therm. Anal, Proc. Int. Conf. 3rd, 1971, (Publ. 1972), 2,651.
H. Klapper and H. Kueppers, Acta Cryst., 1973, 29B, 21.
Elements of Group I
35
and 0.43 + 0.21 eV, respectively. The substantial difference is attributed to

the highest lying orbital in Li20 being largely non-bonding whereas that in
LiO is primarily a bonding orbital. The value of Dg(Lif-0) is comparable
with those of analogous alkali-metal halide ions, i.e. ca. 0.35 eV.220Matrixisolation spectroscopy is being applied to an increasing extent in the study of
species containing the alkali metals. A recent review surveys i.r., Raman,
electronic absorption, luminescence, n.m.r., and e.s.r. spectroscopies as well
as photoionization and electron capture of matrix-isolated atoms, ions, and
radicals. The properties also of matrix-isolated species are discussed.221
Simultaneousmatrix deposition of Li atoms and nitrous oxide at high dilution
in solid nitrogen produccs species which possess the appropriate Li and 0
isotopic shifts for vibrational assignment to the high-temperature molecules
LiO and Li20 which have normally been observed in evaporative studies. The
molecule Li20 is linear, Li-O-Li.222 Using heavier alkali-metal atoms, no
sodium oxides are produced, but the metals K, Rb, and Cs yield products
highwith absorptions appropriate for assignment to v3 of the M-0-M
temperature molecules. These are identified from isotopic shifts and from
experiments involving codeposition of two different alkali metals. K,O and
Rb20 have angles ca. 160-180" whereas that for Cs20 is ca. 130-140".
This trend is rationalized on the basis of increasing metal-metal bonding with
the more polarizable cation. The KO and CsO fundamentals are seen at 384
and 314 cm-l in solid nitrogen.223The standard enthalpy of formation of
Na20(s) at 298 K, calculated from the enthalpy of the reaction of Na20
with hydrochloric acid, is AH; = -100.4 kcal mol-l instead of the previously
reported value of -99. 14.224A second determination, using high-precision
drop-calorimetry, gives two sets of values; one is over the range 298-900 K
and the other from 900 to 1300 K. Two equations are necessary to cover the
entire temperature range since a rapid rise in the heat capacity occurs near
900 K which may be due to a diffusion transition in Na20 accompanied by a
disordering of the Na+ ions. The equations are:
[ H o ( T )- H"(298.15K)]/cal mol-l = 13.8814(T/K)
4.4249 x
(T/K)2 - 4532.09
over the range 298-900 K, and
[H"(T) - H"(298.15K)]/cal mol-l = 35.415(T/K) - 2.80046 x 10-2(T/K)2

1.42549 x 10-5(T/K)3 - 8036.87
over the range 900-1300 K. Using the previously reported value of AH? of
99.14 kcal mol-l, the AG; values are calculated from 290 K (-89.853) to
1300 K (-51.557 kcal m ~ l - l ) The
. ~ ~e.s.r.
~ spectra of molecules of NaO, and
220
a21
222
223
224
225
D. L. Hildenbrand, J . Chem. Phys., 1972, 57, 4556.

D. Milligan and M. E. Jacox, M.T.P. Int. Reu. Sci., Phys. Chem. Ser. 1, 1972, 3 , 1.
R. C. Spiker and L. Andrews, J. Chem. Phys., 1973. 58, 702.
R. C. Spiker and L. Andrews, J. Chem. Phys., 1973, 58, 713.
P. A. G. O'Hare, J . Chem. Phys., 1973,58, 2196.
D. R. Fredrickson and M. G. Chasanov, J. Chem. Thermodynamics, 1973, 5, 485.
4
36
NaSO,, trapped in argon at 4 K following their production by the codeposition of a beam of Na atoms with O2and SO2respectively, comprise a triplet of
quartets. The magnitudes of the Na hyperfine splittings show that each molecule is a bound ion pair. NaO, is a n-radical and NaSO, is non-planar.226In
the oxidation of potassium amalgam, potassium peroxide K,O, is formed.
The rate of oxidation increases with potassium concentration in the amalgam
with temperature and with oxygen concentration in the air. Significantly, the
peroxidation of sodium amalgam is only possible in the presence of potassi~m.~,'
The conditions for preparing sodium superoxide NaO, and potassium
superoxide KO, in THF are reported.228The sodium compound is soluble in
liquid ammonia to the extent of 0.38 at -70 "C to 0.64 g (100 ml NH,)-l
at -40 "C. During the dissolution, however, NaO, partially decomposes to
sodium peroxide, Na,0,.229The burning of sodium is reviewed with regard to
the established rules for metal combustion. A surface layer of oxidized metal
may raise the ignition temperature above that where combustion may theoretically commence. Also included are thermodynamic data for the proposed
constituents of a sodium flame region.230Sodium not only abstracts oxygen
from the air but will also reduce its higher oxides to sodium monoxide, Na,O.
When sodium and sodium peroxide are heated together in argon, ignition
occurs near the m.p. of the metal (98 "C) and is accompanied by explosive
burning, with a transient flame extending from the original sample. The
observed peak temperature is 1120 "C. The overall reaction rate is >1.6
kg mB2s-1.231 This affinity for oxygen is exploited in the preparation of solid
alloys between the solid metals Cu and Th. Sodium does not participate in
the synthesis as a catalyst but very probably reduces the inhibiting surface
oxide on copper, thereby promoting intimate contact and subsequent reaction
between the two solid metals at 200-700 "C to give finely divided and crystalline Th,Cu, ThCu,, ThCu,, and T ~ C U , . ~
The
, ~ Raman spectra of the
polycrystalline compounds NaO,, KO,, RbO,, G O 2 ,KO,, and CsO, have
been measured at 75-300 K. Solid-solid phase-transition effects are observed
in the spectra of the superoxides of Na, K, and Rb, but none is seen with
CsO,. External mode frequencies are observed in the regions 211-200,
146-122, and 89-62cm-l
in the low-temperature spectra of KO, and
RbO,. The spectra of KO, and CsO, exhibit a single band at ca. 1010 cm-l
which is assigned to the symmetrical stretching mode of the ozonide ion
Similarly, the products of matrix reactions of ozone with alkali-metal
atoms on a copper wedge at 16 K show a fundamental absorption at 10111018 cm-l depending on the alkali-metal atom. Substitution of lSO, confirms
226
227
2Z8
229
230
231
282
233
F. J. Adrian, E. L. Cochran, and V. A. Bowers, J . Chem. Phys., 1973,59, 56.

H. Ostertag and Y . Robin-Chassain, Compt. rend., 1973, 276, D, 771.
A. E. Kharakoz, A. G. Kopylova, S. V. Bleshinskii, and 0. Satybaldiev, Fiz-Khim.
Issled. Redkozemel. Elem., 1972, 122 (Ref. Zhur., Khitn., 1973, Abstr. No. 5V15.)
0. Satybaldiev and A. E. Kharakoz, Zhur. neorg. Khim., 1972, 17, 2583.
R. N. Newman, Report 1972, RD/B/N-2229.
R. N. Newman and C. A. Smith, J . Brit. Nuclear Energy SOC.,1973, 12, 117.
B. Berlin, J. Less-Common Metals 1972, 29, 337.
J. B. Bates, M. H. Brooker, and G. E. Boyd, Chem. Phys. Letters., 1972, 16, 391.
Elements of Group I
37
the assignment of these bands to v1 of OF.^^ Further spectral data come from
i.r. (400-4000 cm-l) and Raman (200-1 800 cm-l) studies on polycrystalline
KO, at 77 and 298 K. The band at 1020 cm-l is again assigned to the symmetrical stretching vibration of the 0-0 bonds in the 0;ion. Another band
The thermal
at 818 cm-l is assigned to the antisymmetric 0-0
decomposition of rubidium ozonide, RbO,, produces amorphous rubidium
superoxide, RbO,. The ozonide is monoclinic, space group P2,/c, with
a = 6.44, b = 6.01, c = 8.75A,
= 122', 2 = 4. No phase changes are
observed between -170 and +20 "C.The mixture which results from ozonizing Rb02 contains only the starting material Rb02 and the product RbO,,
without any mutual solid solution.e36In the presence of water at 40-60 OC,
the rate of hydrolysis is greater than the rate of pyrolysis for the ozonides of
potassium, rubidium, and c a e s i ~ m . ~Rubidium
~'
and caesium provide the
greatest range of oxides of the alkali metals. Both metal-rich and oxygen-rich
phases are represented. Thermal analysis and X-ray powder diffraction on the
Rb-Rb20 and Cs-Cs20 systems reveal the extremely air-sensitive compounds Rb60, Rb902,Cs,O, CsIlO,, and Cs,O, with a wide range of stoicheiometry, and CSO,.,,?~~
The compound Rb,O shows physical and chemical
properties which are more characteristic of an alkali metal (electrical conductivity, paramagnetism). It melts incongruently at 46.5 f 1' and crystallizes in the hexagonal system with a = 22.61, c = 14.07 A, d(ca1c) = 2.62,
d(obs) = 2.69 at 30 'C, 2 = 36.239The compound hitherto formulated as
Cs,02 has, according to thermoanalytical and X-ray data, the formula
Csl1O3, and it shows a close structural relation to the compounds Cs,O,
Rb60, and Rb902. The crystals are purple needles which are extremely
sensitive to air and which melt incongruently at 52OC. The compound
CsllO, crystallizes from an excess of metallic caesium and is monoclinic,
space group Pc, with a = 17.610, b = 9.218, c = 24.047 A, = 100.24",
d(obs) = 2.61, d(ca1c) = 2.610,Z = 4. The structure contains discrete Cs,,O,
groups in which the 0 atoms are in a quasitrigonal arrangement, Each 0
atom is surrounded by a distorted octahedron of Cs atoms, The CS,~O,
unit results from face sharing between three CsO, octahedra as shown in
The simultaneous deposition of Cs atoms and 0 atoms at high
dilution in an argon matrix produce species with absorptions in the i.r. at
1115, 268, and 236 cm-l. These are assigned to vl, v,, and v2, respectively, of
the Cs+O;i-species. The use of isotopic mixtures of oxygen confirms these
assignments and the isosceles triangular structure for CsSOz. The most
234
235
L. Andrews, J . Amer. Chem. SOC.,1973, 95,4487.

A. I. Karelin, V. Ya. Rosolovskii, S. A. Tokareva, and I. I. Vol'nov, Doklady Akad.
Nauk S.S.S.R., 1972, 206, 641.

236
237
M. S. Dobrolyubova, V. Ya. Dudarev, V. A. Sarin, and A. B. Tsentsiper, Izvest.

Akad. Nauk S.S.S.R., Ser. khim., 1973, 146.
A. B. Tsentsiper and M. S. Dobrolyubova, Izvest. Akad. Nauk S.S.S.R., Ser. khim.,
1972, 1471.
238
23B
MJ
A. Simon, 2.anorg. Chern., 1973,395, 301.

P. Tozain, Bull. SOC.chim. France, 1972,4515.
A. Simon and E. Westerbeck, Angew. Chem. Internat. Edn., 1972, 11, 1105.
38
I=
caesiurn
a = oxygen
intense absorption for Css02,-Css is observed at 357cm-l. The i.r. and

Raman (R) spectral data for all the C2, alkali-metal superoxide molecules in
an argon matrix at 15 K are shown in Table 6 . A strong band at 1002 cm-l,
Table 6 I.r. and Raman ( R ) data for alkali-metal superoxides (wauenumberslcm-I)

Molecule
Vl
v2
vs
6Li0,
1097.4
1097.O(R)
1096.9
1 096.6(R)
1094 (R)
1108 (R)
1111.3
1110 (R)
1115.6
1114 (R)
743.8
740 (R)
698.8
694 (R)
390.7
307.5
255.0
507.3
236.5
268.6
LiO,
NaO,
KO,
RbO,
CsO,
492.4
332.8
282.5
which shows isotopic splittings for a species containing two 0, molecules, is

assigned to Cs+Or. The vibrational data, however, do not allow a detailed
assignment of the structure of this species to be made.241
7 Alkali-metal Halides
Sodium halides are extensively covered in two supplementary volumes of
Gmelins Handbook of Inorganic Chemistry published in 1972.2421243
Several
alkali-metal halides have been investigated by the relatively new technique of
photoelectron spectroscopy. This technique forms the basis of several
343
243
L. Andrews, J. T. Hwang, and C. Trindle, J. Phys. Chem., 1973, 77, 1065.

Gmelins Handbook of Inorganic Chemistry, System No. 21 : Sodium, Supplementary
Volume, Sect. 6: Sodium Halides. 8th edn., 1972.
Gmelins Handbook of Inorganic Chemistry, System No. 21 : Sodium, Supplementary
Volume, Sect. 7: Sodium Halides. 8th edn., 1972.
Elements of Group I
39
instrumentation is also covered.249*250

Basically, a core
electron of an atom in a compound is expelled by a beam of X-rays, U.V.
light, or electrons of known energy. The kinetic energy of the ejected electron
is measured and its binding energy deduced by difference. The binding energy
is, in many cases, sensitive to the chemical state and environment of the
atom. Binding energies for Li Is, Na Is, K 2p3/2,Rb 3d, C s 3d55/2,F Is,
C1 2p, Br 3d, and I 3d5/,have been measured, when appropriate, in alkalimetal halides. The range of binding energies is narrow (within 2 eV) for each
of the alkali metals in the various salts whereas a somewhat greater range
(ca. 3 eV) is found for the halogens. The variations in the experimental binding
energies of these salts parallel those in the respective orbital energies
calculated for the gaseous diatomic molecules in a near-limit Hartree-Fock
equation.251Ionization potentials for the removal of various electrons from
the alkali-metal chlorides and the sodium and potassium halides are compared
with the predictions of a simple point-charge model with and without
corrections for polarization and repulsion. The data show, and the model
predicts that, the spacings of the energy levels for a given ion are independent
of which crystal the ion is in and are the same as those for the free ion. There
is, however, a disagreement between the predicted and experimental values
of the difference between cation and anion energy levels in the same crystal,
ranging from ca. 1.8 eV for LiCl to -0.2 eV for RbCl. This discrepancy is
markedly reduced by inclusion of polarization effects.252A simple analysis of
the photoelectron spectra of alkali-metal halides yields partial rather than
unit charges on the ions. The difference between the binding energies of the
electrons of the cation and anion when calculated on a completely ionic
basis is always in error by ca. 1 eV in comparison with experimental data.
Such discrepancies may be due to covalency except in the most ionic compounds CsBr and C S I .Recently
~ ~ ~ obtained data on doubly ionized rubidium
in the free state indicate that the satellite of the Rb (4s) resonance in the
photoelectron spectra of RbF and RbCl is primarily due to a 4s24p44d2S
state rather than one of 4s24p45s2S.For the potassium salts, the satellite of
the K(3s) resonance is most likely due to a 3s23p43d2$final state. The absence
of a satellite for the sodium salt is due to the non-existence of 2d electrons.254
The hyperfine-structure constants, rotational constants, and other molecular
parameters have been tabulated separately for each vibrational and rotational
a46
247
248
24g
z60
261
252
263
254
A. D. Baker, C. R. Brundle, and M. Thompson, Chem. SOC.Rev., 1972,1,355.

K. Siegbahn, Endeavour, 1973,32, 51.
D. A. Shirley, Adv. Chem. Phys., 1973, 23, 85.
K. Siegbahn, Electron Spectrosc. Proc. Int. Conf., 1971 (Pub. 1972), p. 15.
T. A. Carlson, Electron Spectrosc. Proc. Int. Conf., 1971 (Pub. 1972), p. 53.
C. A. Lucchesi and J. E. Lester, J. Chem. Educ., 1973, 50, A205-6.
R. D. Davies, H. K. Herglotz, J. D. Lee, and H. L. Suchan, Ado. X-Ray Analysis,
1973, 16,90.
W. E. Morgan, J. R. Van Wazer, and W. J. Stec, J. Amer. Chem. SOC.,1973,95,751.
T . D. Thomas, J. Chem. Phys., 1972, 57,4446.
D. E. Parry and M. Tricker, Chem. Phys. Letters, 1973, 20, 124.
J. Reader, Phys. Rev. (A), 1973, 7 , 1431.
40
eigenstate for MX, MH, MD, HX, DX, TX (M = 6*7Li,23Na,39K,*5Rb,
lSCs, 27Al,69Ga,l151n, or ,05Tl, X = leF, 35,37C1,79,81Br,or 1271)as well as
for various diatomic halides and/or hydrides of ,lK, 87Rb,loJIB, 71Ga, and
,03Tl. The values are selected from papers published during 1919-1971.
The results listed are generally determined by either microwave or molecular
beam spectroscopic techniques. Data from n.m.r. spectroscopy, electron
diffraction, and X-ray diffraction are excluded.255Measurements of the
electrical conductivity of KC1, KBr, and KI vapour at 850 "Cand 750 mmHg
indicate that an equilibrium dissociation of the compounds into ions takes
place below the plasma temperature (2000-3000 "C) without the application
of an external ionization source.256A mass spectrometric analysis of the
vapours of the compounds LiF, NaF, and K F reveals the presence of the
molecules LiF, Li2F2,and Li,F,, NaF, NazF2,and Na3F3,and KF and K,F,,
re~pectively.~~'
The molecular parameters of the orthorhombic alkali-metal
dihalide molecules M2X2have been deduced from the relationship which
holds for Li,X, :
r,(M-X) = 1.075r,(M-X)
where r,(M-X) is the internuclear distance in the monomeric molecule ( 1 1).
Vibrational frequencies and thermodynamic functions for the dimeric molecules are subsequently evaluated. The internuclear distances and angles for
(11)
the dimers are shown in Table 7 . The values for Li,X2 are from previously
reported experimental data.,S8
Mass spectrometry of the LiF-GaF, system shows that molecules of LiF,
Li2F2,and Li,F, as well as those of LiGaF,, (LiGaF,),, Li,GaF,, and GaF,
exist in the saturated ~ a p o u rSome
. ~ ~ lattice
~
energies for alkali-metal halides
are KC1 168.8, KBr 156.0, KI 139.0, and RbCl 158.5 kcal mol-l. The lattice
energies for KBr-KI or KCl-RbC1 solid solutions are lower than values
calculated on the basis of additivity.260The activation energies, E, of ionic
conduction in alkali-metal halides can be correlated with lattice energies, UL.
For common cations, the relation is E/eV = 0.35 (VJeV) - a ; a is 1.53,
a55
a56
258
259
280
C. E. Miller, A. A. Finney, and F. W. Inman, At. Data, 1973, 5 , 1.

N. L. Yarym-Agaev and V. G . Matvienko, Dopouidi Akad. Nauk Ukrain R.S.R., Ser
B, 1972, 34, 741.
A. S. Alikhanyan, V. B Shol'ts, and L. N. Sidorov, Vestnik Moskov. Univ., Khim.,
1972, 13, 639.
K. S. Krasnov, V. G . Solomonik, and E. V. Morozov, Teplojz. Vys. Temp., 1972,10,
760.
L. N. Sidorov, N. A. Zheful'skaya, and M. V. Korobov, Zhur.fiz. Khim., 1973, 47,
1336.
E. K. Zavadovskaya, K. S. Cholokov, and V. A. Grishukov, Khim. Suyaz Poluprou.
Polumetallakh, 1972, 204.
Elements of Group I
41
Table 7 Values of internuclear distances and angles for dimers of alkali-metal

halides
Molecule ra(M-X)/A
LXMX/"
LiaF2
Li2C12
Li2Br2
Li212
Na2F2
Na,C12
Na2Br2
Na2L
KZF2
KzC12
Ka-2
K2Iz
RbzFz
RbzCl2
Rb2Br2
RbaL
CsaFa
CS,Cl,
Cs2Br
CS212
1.68
2.17
2.35
2.54
2.1 1
2.54
2.69
2.92
2.34
2.84
2.03
3.28
2.44
3 .oo
3.17
3.41
2.52
3.12
3.30
3.56
104
108
110
116
100
109
111
114
92
101
104
107
88
98
100
104
82
94
96
99
0.95, 0.43, and 0.24 for Li+, Na+, Kf, and Rb+, respectively. For common
anions, E - 3.02 = -b(UL - 4.83); b is 0.16, 0.46, 0.37, and 0.64 for
F-, C1-, Br, and I- respectively.2s1
Contrary to existing data, LiCI,H,O is orthorhombic with a, c = 7.68,
b = 3.87 A and a probable space group C r n ~ r nThe
.~~
thermal
~
decomposition
of LiX,nH,O and LiX,nD,O (X = Cl, Br, or I; n = 1, 2, or 3) has been
studied using a thermobalance. The dehydration of LiCl,H,O, LiCI,D,O,
LiI,3H20, and LiI,3D20 occurs in two stages, with the hemihydrates as
intermediates. The compounds LiX,2H20 and LiX,2D20 (X = Br, C1, or I)
give sesquihydrates as intermediates. The thermal stability of the compounds
decreases with increasing water content and the deuterates are more stable
than the hydrates.263The solubility in water of LiBr and LiI at 303-332 K
increases with increasing temperature. For LEI, however, the solubility first
increases (296-335 K), is nearly constant (310-322 K), and then increases
again. At a particular temperature the solubility decreases in the order
LiCl > LiBr > LiI. The enthalpies of solution, AH, are 1.85-1.88,0.4522.308, and 0.89-3.41 kcal mol-l, respectively, for LiCl, EiBr, and LiI,
as calculated from the solubility data. With increasing temperature, AH is
essentially constant for LiCI, decreases for LiBr, and passes through a
minimum at ca. 316 K for LiI.264The vibrational spectrum of a single crystal
of RbIC1, varies continuously with temperature from 40 to 295 K. The
261
262
263
264
S. Mizuta and H. Yanagida, Denki Kagaku, 1972,40,616.

H.Jacobi, Acfa Cryst., 1972,28B, 3106.
M.Manewa and H. P. Fritz, 2.anorg. Chem., 1973,396,279.
M. Afzal and N. P. Chaudry, Pakistan J. Sci. Res., 1971,23, 134.
42
spectrum confirms the linearity of the ICI, ion in this crystal of Dii-Pnrna
symmetry.265The solubility of Group I-VI element fluorides in hydrogen
fluoride has been
A very large number of complex halides containing the alkali-metal ions
have been investigated. Many of these are covered in the section on Molten
Halides. The majority of the remainder are presented in Table 8.
The crystal structures of compounds with composition ABX, and A,BX6
are shown to originate from a basic lattice by using mainly qualitative ionic
bonding rules (A represents a large cation that can replace an anion, B is a
small interstitial cation, and X is halogen). The ideal structures (i.e. for A and
X ions of equal radius) for hypothetical compounds AX are derived. If A-A
contacts are not allowed in close-packed layers of halogen, then each layer
must have the composition AX, and the same type of order, which can be
one of two simple types or any combination of these. From these AX,
structures those of ABX, and A2BXs are derived. Finally, the deviations
from the ideal ABX, and A,BX, structures resulting from variations in size of
the A, B, and X ions are considered.267The published data are presented and
discussed in a review of the binary systems A-B, where A is MF (M = Li,
Na, K, Rb, or Cs) and B is BeF,, SnF,, AIF,, GaF,, LaF,, ScF,, YF,, VF,,
ZrF,, HfF,, or VF,. Following the energetic characteristics of the complexes,
schemes of the structures are given, and structures which are compatible with
mass spectral data are proposed for the A,B and A,B, types. Complex
molecules of the AB, A,B, and A,B, types exist in the vapour phase.268
8 Lithium Compounds
The reactions of atoms and small molecules as studied by u.v., vacuumu.v., and visible spectroscopy are discussed in a review which covers rate
constants for addition and recombination reactions of molecules and atoms
(includes Na, K , and Rb); collisional cross-sections; rate constants for
reactions and energy transfers of recently observed diatomic molecules and
radicals (includes
The properties of saline hydrides (and metallic hydrides) and their corresponding deuterides and tritides of possible interest to controlled-fusion
reactor technology are reviewed. The topics include the lithium-hydrogen
system and the solubility of H, D, and T in metals.290Single crystals of
lithium hydride can be grown by a method that was proved successful for
lithium fluoride;291the lattice energy as calculated from elastic constants and
Debye temperature is UL = 221.8 kcal m01-1.292 In many ways lithium
hydride resembles an alkali-metal halide and can be handled in the molten
265
a66
267
M*
J. P. Coignac and M. Debeau, Compt rend., 1972,275, B , 211.

D . D. Ikrami, A. S. Paramzin, and Kh. Sh. Dzhuraev. Izuest. Akad. Nauk Tadzh.
S.S.R., Otdel. Fiz-Mat. GeoLKhim. Nauk, 1972, 42.
A. B. A. Schippers, V. Brandwijk, and E. W. Gorter, J. SoIidState Chem., 1973,6,479.
V. B. Sholts and L. I. Sidorov, Vestnik Moskov Univ., Khim., 1972, 13, 371.
43
Elements of Group I
Table 0 Complex halides that have been iizvestigated

Ref.
Cornpourid
For MF(s) BF,(g) B+MBF,(s), A H = 269

-31.3, -39.9, -44.3, -47.2, and -52.9
kcal mol-1 for M = Na, K, Rb, Cs, and
Ba, respectively.
270
MBC14 (M = K , Rb, or Cs)
AG;,, = -196 f 2, AH19, = -219.9 f 0.4,
KBCl,
27 1
U, = 121 kcal mol-l
AG;,, = -201 & 2, AHZOg, = -222.8 f 0.5,
RbBC14
27 1
U, = 117 kcal mol-1
AG;~, = -202 f 2, AHi9, = -225.3 f 0.5,
CsBC14
27 1
UL = 113 kcal mol-l
NaF,B20S
272
m.p. 660 "C
NaF,2B2O,
m.p. 640 "C
272
273
LiAlF4
273
NaAlF,
11NaF,4AIF,,H20
decornp. 930-940 "C
274
monoclinic, space group P2,/c, a = 12.732, 275
KAl,Br7
b = 10.822, c = 14.444A, /3 = 133.87",
Z = 4, d(ca1c) = 3.107. The A1,Br:- anion
consists of two AlBr, tetrahedra sharing one
corner. K surrounded by nine Br at 3.34.0 A.
276
space group P213; M = Li, a = 5.138 A,
MAlOCl,
Z = 1.4
M = Na, a = 5.630 A,
Z = 1.7
M = K, a = 6.267 A,
2 = 2
Cubic close-packed Cl- ions with octahedral
interstices occupied by (K Al) ions; half
of tetrahedral interstices occupied by 02ions.
cc-Rb31nF6,tetragonal, a = 6.513, c = 9.260 A 277
M,InF, (M = Rb or Cs)
cc-Rb31nF6,cubic, a = 9.249 A
a-Cs,InF6, tetragonal, a = 9.51, c = 9.61 A,
d(exp) 4.83, d(ca1c) 4.80,Z = 4
&Cs,InF,, cubic, a = 9.63 A
MBF,
269
270
F. Kutek, Sb. Vys. Sk. Chem-Technol. Praze, Anorg. Chem. Technol. 1972, B14, 77.
K.V. Titova, I. P. Vavilova, and V. Ya. Rosolovskii, Zhur. neorg. Khim., 1973, 18,
271
1131.
N. V. Krivtsov, K. V. Titova, and V. Ya. Rosolovskii, Zhur. neorg. Khim., 1973, 18,
347.
272
273
274
275
276
277
V. M. Pavlikov, V. 0.Yurchenko, and I. E. Kir'yakova, Dopovidi Akad. Nauk Ukrain.

R.S.R., Ser. B, 1973,35, 540.
A. Snelson, S. J. Cyvin, Z . anorg. Clzem., 1972, 390, 316.
S. A. Frolkova, G. E. Dmitrevskii, F. V. Makordei, and V. D. Chugunov, Izuest. I/.
U.Z., Khim. i khim. Tekhnol., 1973, 16, 6.
E. Rytter, B. E. D. Rytter, H. A. Oye, and J. Krogh-Moe, Acta Cryst., 1973,29B, 1541.
V. G. Kuznetsov, S. I. Maksimova, and A. I. Morozov, Zhur. strukt. Khim., 1973, 14,
483.
J. Grannec, J. C. Champarnaud-Mesjard, J. P. Costy, J. C. Cousseins, and B. Gaudreau, Rev. Chim. min&ale, 1972, 9, 569.
44

Table 8 Complex halides that have been investigated (contd.)
Compound
MInF, (M = Rb or Cs)
Na,SiF, ,KSiF6
Li2SnF,,2Hz0
Rb,SnC&
CsSnC1,
Cs,SnCI,
K,Sb,Clg
K3Sb,Br9
K2SbI5
Rb3SbzIs
Cs,Sb,I,
2KCl,BiCl,
3KCl,BiCI,
CsBiF,
Rb,TeCl,
MHF,
Ref.
a-RbInF,, orthorhombic, a = 8.268, b = 278

8.082, c = 13.105 A, d(exp) = 4.29, d(ca1c)
= 4.20,Z = 8
a-CsInF,, orthorhombic, a = 8.089, b =
6.782, c = 8.103 A, d(exp) = 4.77, d(ca1c)
= 4.83, Z = 4
278
monoclinic, space group C2/m, a = 9.813, 279
b = 6 . 1 0 1 , ~= 4.7278,,/3 = 90.96",2 = 2,
d(exp) = 3.40, d(ca1c) = 3.26
U, 342 =t 17 kcal mol-1
280
High temp. CsSnCl, cubic, a = 5.504 A, m.p. 28 1
375"C, decomp. 600C Low temp.
CsSnCl,, triclinic.
decomp 217 "C
28 1
triclinic
monoclinic, space group P2,/c, a = 22.37, 282
b = 8.17, c = 13.09 A, /3 = 124"32',
d(exp) = 3.68, d(ca1c) = 3.66.
Decomposes to KI and volatile SbI,
283
Decomposes to RbI and SbI,
283
Decomposes to CSI and Sb13
283
284
284
No evidence for BiF; ion in H F solution by 285
Raman spectroscopy
cubic, a = 10.233 A, d(exp) = 3.08, d(ca1c) = 280
3.16, Z = 4 UL= 334 f 17 kcal mol-1
M = Li, Na, K, Rb, or Cs
286
LiHFz, UL = 820.6; NaHF,, UL= 755.3;
KHFS, U L = 648.2; RbHFz, UJ = 626.9;
CsHF,, U, = 607.4 kJ mol-l.
orthorhombic, space group Pbarn, a = 8.258, 287
b = 11.662, c = 8.925 A, Z = 4.
monoclinic, space group C,Z - P21, a = 11.30, 285
b = 7.94, c = 8.46 A, y = 110"27', Z = 2
D. R. Howlett, J . Appl. Cryst., 1972, 5 , 378.

E. A. Marseglia and I. D. Brown, Acta Cryst., 1973, 29B, 1352.
2 8 0 M. Webster and P. H. Collins, J. C. S. Dalton, 1973, 588.
281 G. G. Bulanova, A. V. Podlesskaya, L. V. Soboleva, and A. I. Soklakov, Zzuest.
Akad. Nauk S.S.S.R.,Neorg. Materialy, 1972, 8, 1930.
282 M. B. Varfolomeev, G. V. Zimina, T. G. Dar'ina, and V. E. Plyushchev, Izuest. V. U.
Z., Khim. i khim. Tekhnol., 1973, 16, 674.
0. P. Molchanova, G. V. Zimina, S. B. Stepina, andV. E. Plyushchev, Izoest. V. U.Z . ,
Khim. i khim. Tekhnol., 1972,15, 1281.
z84 V. D. Shcheglova, S. B. Stepina, V. E. Plyushchev, and A. S . Berger, Izvest. sibirsk.
Otdel. Akad. Nauk S.S.S.R., Ser. khim. Nauk, 1972, 123.
Zs5 T. Surles, L. A. Quaterman, and H. H. Hyman, J. Inorg. Nuclear Chem., 1973,35, 670.
m6 H. P. Dixon, H. D. B. Jenkins, andT. C. Waddington, J. Chem. Phys., 1972,57, 4388.
287 K. Aurivillius and C. Stalhandske, Acta Chem. Scand., 1973,27, 1086.
2P8 V. I. Pakhomov and P. M. Fedorov, Kristallograjya, 1972, 17, 942.
279
Elements of Group I
45
state. In this respect, it differs from the other alkali-metal hydrides, which
dissociate before melting. Thus LiH, LiD, and LiT can be cast in the molten
state into a titanium-coated mould provided that a hydrogen blanket is used
at a pressure adequate to saturate the titanium. The LiH, LID, and LiT
prepared by this process are suitable for use as moderators for nuclear
reactors and neutron shields.293The exchange process for the reaction
between D gas and LiH single crystals has been studied as a function of D,
pressure over the range 85-555 Torr at 465 "C.The kinetic data are fitted
best by considering the rate of the exchange process to be controlled by the
diffusion of D-. By using solutions to Fick's second law and considering the
surface concentration of D to vary with pressure, the diffusion coefficients
are found to be independent of pressure. The tracer diffusion coefficients
thus found are 1.4 x 10-9cm2s-1, for a one-dimensional model, and
1.9 x
To determine H, D ,
cm2s-l, for a three-dimensional
and T in LiH-LiD-LiT mixtures, a sample (ca. 1 g) is thermally decomposed
in the presence of Pb to give isotopic H, which is oxidized with CuO at 450 O C
to give isotopic water for spectrophotometric analysis. Alternatively, a 50 mg
sample is hydrolysed under vacuum with H20or D20to give LiOH or LiOD,
respectively, and isotopic H for gas chromatographic, i.r., or mass spectrometric analysis. Upon hydrolysis with H20, nitrogen which is present as
Li,N, Li2NH, and LiNH2 is converted into hydroxylamine, which is determined by potentiometric titration with HCl. To determine Li, the LiOH
formed by hydrolysis of the sample is titrated potentiometrically with HCl
after NH, is removed by distillation and trapping at liquid-nitrogen temperatures. To determine oxygen present as Li,O, LiOH, LiOD, or LiOT, the
sample is treated with acetic acid in MeOH and the H20formed is determined
with Karl Fischer reagent. The oxygen present as Li2C0, is converted by
HOAc into C 0 2 for determination. To determine C as Li,C, or Li2C0,,
the sample is decomposed at 1000C in an oxygen stream to give C02,
which is determined electrochemically by absorption in Ba(OH), s o l ~ t i o n . ~ ~ 5
The structures of the gaseous molecules MB02 (M = Li, Nay K, or Rb)
have been determined by electron diffraction at 1200-1600 K. A linear
arrangement of the OBO group is established, with M-0 distances of 21.4 f
0.03, 2.36 f 0.03, and 2.54 f 0.02 8, for Na, K, and Rb, respectively.2g6A
selection of previous work on the structure and properties of LiAlH,,
Li,AlH,, and LiA12H, is summarized.297The crystal structure of Li,AlH,
is monoclinic, a = 7.892, b = 8.096, c = 5.650, B = 91.83', d(expt) = 0.994,
289
2B0
291
292
293
2S4
296
298
297
R. J. Donovan and D. Husain, Ann. Reports (A), 1971 68, 123.

G . G. Libowitz, Cliem. Fusion Technol., Proc Symp , 1972, 321.
C. E. Holcombe and D. H. Johnson, J. Cryst. Growth, 1973,19, 53.
G. Terras, Report 1973, CEA-R-4409.
E. C. Phillips, U.S. P. 3 692 888 (Cl. 264/.5R; G21c), 1972.
D. S. Catlett, J. N. Spencer, and G . J. Vogt, J. Chem. Phys., 1973, 58, 3432.
H. Lefevre, G. Reversat, and J. C. Putaux, BUN.Inform. Sci. Tech., Commis. Energ. At.
(Fr.), 1973, No. 178, p. 51.
Yu. S. Ezhov, S. M. Tolmachev, and N. G. Rambidi, Zhur. strukt. Khim., 1972,13,972.
J. Mayet and J. Tranchant, Bull. SOC.chim. France, 1973, 510.
46

d(ca1c) = 0.991 for Z = 4, space group P2,lm. The decomposition:
Li,AlH, -+ 3LiH A1 +H2
+ +
occurs at ambient temperatures.298A new and convenient method is described

for the preparation of complex metal hydrides containing lithium or sodium
or potassium. Thus LiZnH,, Li,ZnH,, and Li,ZnH, are prepared by allowing
LiAlH, to react with Li,ZnMe,+, (n = 1-3). The hydrides LiAlH, and
NaAlH, reduce M,ZnR,+, (M = K or Na; R = alkyl) to give KZnH,,
KZn2H5,and NaZnH,.2g9
Small amounts of lithium carbide, Li,C,, suitable for use in radio-dating,
are prepared at 700 C by the reaction:
2CaC0,
+ lOLi +Li2C2+ 2Ca0 + 4Li20
The optimum yield is obtained by employing excess Li metal (15 % above the
stoicheiometric amount).300The spectrum of lithium isocyanide trapped in
solid matrices of Ne, Ar, and N has been examined over the range 40004033 cm-l. Temperature cycling results in migration of trapped molecules to
generate polymeric species. Isotope frequency shifts measured for 13C-,
15N-,and 6Li-enrichedsamples indicate that the monomer, LiNC, is linear.301
New alkali-metal silicates are prepared by heating the appropriate binary
oxides in a silver bomb at 400--700C. Thus Li,Si06 crystallizes in the
hexagonal form, space group P6cm, with a = 5.42, c = 10.63 A, 2 = 2. For
M6Si20, (M = K , Rb, or Cs) the lattice constants for the monoclinic phases
are (M = K) a = 6.459, b = 8.886, c = 11.13 A, = 126.8; (M = Rb)
a = 6.755, b = 9.205, c = 11.52A, /3 = 126.9; (M = Cs) a = 7.143,
b = 9.533, c = 12.03 A, and /3 = 126.6.,O2 The crystal structure of Li2Si,05
has been redetermined. The compound is orthorhombic with a = 5.834,
b = 14.672, c = 4.791 A and space group Ccc2. The SiOBtetrahedra are, as
before, linked by vertices in Si,O, pairs which form infinite two-dimensional
corrugated layers. The lithium atoms are located in cavities between these
layers. The alternation of empty cavities and ones filled with lithium atoms,
however, is different from what was presumed. Surrounding the Li atoms
are four 0 atoms of SiO, tetrahedra (three terminal and one bridging 0 atom,
with Li-0 distances 1.940-2.055 A) which form a distorted tetrahedron
around lithium.,03The compounds Li2CaSi0, and Li,CaGeO, are isostructural
and possess body-centred tetragonal unit cells with dimensions a = 5.047,
5.141 ;c = 6.486, 6.595 A, respectively, and space group I42m. In Li,CaSiO,,
lithium is situated at the centres of distorted (Si0,)- tetrahedra which share
corners to form two intersecting sets of chains. These comprise rather open,
298
20g
300
301
308
303
J. Mayet, S. Kovacevic, and J. Tranchant, Bull. SOC.chim. France, 1973, 503.

E. C. Ashby and J. Watkins, J. C . S. Chem. Comm., 1972, 998.
0. B. Parunin and I. V. Grakova, Radiouglerod, Muter. Vses. Soveshch. Probl. Variatsii Soderzh. Radiougleroda Atmos. Zemli Radiouglerodnoe Datirovanie, 1971, 185.
Z. K. Ismail, R. H. Hauge, and J. L. Margrave,J. Chem. Phys., 1972,57,5137.
W. Schartau and R. Hoppe, Naturwiss., 1973, 60,256.
Yu. I. Smolin, Yu. F. Shepelev, and A. P. Titov, Yrobl. Kristallologii, 1971, 149.
Elements of Group 1
47
two-dimensional sheets of constitution (Li204)6-, in which all the corners,
but no edges, of the tetrahedra are shared. Adjacent sheets are joined, via
silicon, by sharing corners with (sio4)4- tetrahedra, and also via calcium in
distorted dodecahedra, (CaO,)l*-. Comparison of Li,CaSiO, with other
oxides containing tetrahedrally co-ordinated lithium shows that the (LiO,)tetrahedra are quite versatile in the ways they can coalesce. Thus Li,O has a
three-dimensional antifluorite structure with all tetrahedral edges shared and
in Li,PdO, four of the edges in each tetrahedron are shared.304The preparation and properties of a lithium hydride nitride Li4NH are reported. The
compound is tetragonal with a = 9.87, c = 9.70 A, d(expt) = 1.20, d(ca1c) =
1.20 for 2 = 16. The preparation consists of heating lithium nitride to 500 O C
with dry low-pressure hydrogen or, alternatively, with lithium h~dride.~O5
The crystal structure of lithium amide has been redetermined by singlecrystal X-ray methods. The amide crystallizes tetragonally, with a = 5.037,
c = 10.278& 2 = 8 and space group 14. The anions are arranged in a
distorted cubic close packing. The Li+ ions occupy the tetrahedral interstices.
This unusual distribution of the cations is explained by the orientation of the
NH; ions in the lattice, as shown in Figure 4.306Trilithiumtrisulphimide
= NH2
Figure 4 The tetrahedral environment of Li+ in LiNH,

~4
305
306
J. A. Gard and A. R. West, J. Solid State Chem., 1973,7,422.

J. F. Brice, J. P. Motte, and J. Aubry, Compt. rend., 1973, 276, C, 1015.
H. Jacobs and R. Juza, 2.anorg. Chem., 1972,391,271.
48
(1,3,5-trilithium-2,4,6-trithiatriazine1,1,3,3,5,5-hexoxide) is prepared by the

reaction of LiOH,H,O with (NH,,NSO,), in the solid state or by using
high-boiling alcohols as the reaction medium. The depolymerization process
c Li3(NSO&,H20 + 3NH3 + 5Hz0
\y
(NHJa(NSO& + 3LiOH,Hs0
77
bLi@TSO&
+ 3NH3 + 6Hz0
to the monomer, which would contain the imido-dioxosulphate(w) ion, does

not occur since the monomer is unstable. Instead, on heating above 360 O C ,
thermolysis occurs according to :307
(M = Li, Na, or K)
Matrix reactions in solid argon of Li atoms with NO have been investigated

using approximately equimolar concentrations of the reactants at high
dilution. Intense bands at 1352 and 651 cm-l and isotopic counterparts are
assigned to intraionic (N-0)- and interionic Li+-(NO)- vibrational modes.
Mercury arc photolysis decreases the 651 cm-l band while the 1352 cm-l
band increases, and a new 447cm-l band appears. This suggests photoisomerization of the triangular Li+-(NO)- species to another in which the
interionic Li-0 frequency is shifted to 447 cm-l but the (NO)- frequency
remains the same. Absorptions at 886, 769, and 415 cm-l are assigned to the
secondary reaction product Li+(N0)2-Li+; the 886 cm-l wavenumber is
primarily an intra-ionic (NO)2- mode whereas the latter two frequencies are
interionic modes.308The compound LiSi,N, has a wurtzite-type tetrahedral
structure; the crystals are orthorhombic, space group Cmc2,. The N atoms
are arranged in a slightly distorted hexagonal close-packing. The Li and Si
atoms are ordered among one half of the tetrahedral sites in the hexagonal
p a ~ k i n g . 3The
~ ~ ternary lithium phosphides Liz,+3MnPn-l (M = beryllium,
cadmium, or tin) have the antifluorite or derived structure, The crystallographic parameters u/A, experimental densities, and calculated densitieslg
cmM3,respectively, are: Li,SnP, (2 = 413) 5.97, 2.57, 2.56; Li,SnP, (space
group T:) 11.95, 2.32, 2.33. In Li,SnP3, the cations statistically occupy the
tetrahedral sites. In Li,SnP,, the Sn atoms are ordered on the tetrahedral
sites but the excess Li atoms are in the octahedral sites.310The phase equilibria
308
309
E. Nachbaur and E. Baumgartner, Monutsh., 1973,104,1131.

D.E. Tevault and L. Andrews, J . Phys. Chem., 1973,77, 1640.
J. David, Y. Laurent, J. P. Charlot, and J. Lang, Bull. SOC.franc. Mineral. Crist.,
310
A. El Maslout, J. P. Mo tte, and C. Gleitzer, J. Solid State Chern., 1973,7,250.
307
1973,96,21.
Elements of Group I
49
in the systems M2S-Sb,S, and M,SeSb,S, (M = alkali metal) as studied by

d.t.a. show the presence of the compounds (with m.p./"C); LiSbS,, 670;
Na,SbS,, 600; Na,SbSg, 615; KSbS,, 510; RbSbS,, 460; CsSbS,, 400;
LiSbS,, 720; NaSbSe,, 730; and KSbS,, 510.311The structure of lithium
sulphate has been redetermined. The compound is monoclinic, P2,/c,
a = 8.45, b = 4.95, c = 8.21 .$,/3 = 107.5",2 = 4, d(exp) = 2.23. Crystals
were grown from a melt of Li2S0,. The Li+ ion is tetrahedrally co-ordinated
with a mean Li-0 distance of 1.96 .$, and the mean S-0 distance is 1.472 8,
in the SO$- tetrahedra.,12 A new crystal phase, lithium tellurate Li,Te,O,,
has been found in the Li20-Te0,-Te03 system. The crystallographic parameters of the triclinic compound are a = 5.186, b = 7.766, c = 5.122 A,
o! = 101.95",
= 101.88", y = 107.61, d(expt) = 3.66, d(ca1c) = 3.56 for
2 = 1. The compound is prepared in microcrystalline form by heating Li,TeO,
under vacuum at ca. 580 "C. By heating Li,Te20, in air, Li,TeO, is formed at
550-600 "C, and at 750 "C Li,TeO, is produced.313
9 Sodium Compounds
The reaction of deuteriated water vapour with alkali-metal mirrors has been
investigated at 23C. From flow experiments it is established that every
collision of a water molecule with the surface results in reaction. Hydrogen is
liberated. In static experiments enrichment of H over D in the evolved gas
occurs in the order of effectiveness Na = K < Li < Rb = Cs. The isotope
fractionation and composition of the molecular hydrogen which is produced
are independent of the metal:H,O ratio when metal is in excess. Under these
conditions the expression [HDI2/[H,][D,] = 12.0 f 2.6, which is well above
the value of the equilibrium constant of 3.85 at 298 K. The value is also
independent of the alkali metal. These results are in accord with a model in
which the metal reacts with a water molecule to form the alkali-metal hydroxide and an adsorbed H atom. In order to yield molecular hydrogen, this
adsorbed atom transfers by quantum-mechanical tunnelling to react with
another adsorbed hydrogen atom.314 At 400 "C, liquid sodium (20 g) reacts
with molten sodium hydroxide (500 g) to form sodium hydride and sodium
monoxide. The sodium hydride partially dissociates under these conditions
to produce gaseous hydrogen. The rate of reaction of the metal with hydroxide
is judged by the rates of accumulation of sodium hydride and of hydrogen.
The reaction:
2Na
+ NaOH = Na,O + NaH
is reversible, but under these conditions the metal is almost quantitatively

converted into Na,O and NaH. The latter dissolves in the excess of unreacted
311
31a
313
314
V. B. Lazarev, S. I. Berul, and A. V. Salov, Therm. Anat., Proc. Int. Con$, 3rd, 1971
(Pub. 1972), 2, 171.
N. W. Alcock, D. A. Evans, and H. D. B. Jenkins, Acta Cryst., 1973,29B, 360.
J. Moret, A. Norbert, and D. Cachau-Herreillat, Compt. rend., 1973, 276, C,677.
R. 0. Bremner and D. H. Volman, J . Phys. Chem., 1973,77,1844.
50
NaOH and gives virtually no hydrogen in the gas phase. The rate of the
reaction is given by:
dc
- = 0.0355 - 0.016~
dt
where dcldt is the number of moles of hydride formed per hour per square
centimetre and c is the concentration/mole% of hydride in the melt.315 In
the thermal decomposition of NaAlH,, the complex hydride first melts, at
185-190 "C, and decomposition begins at 250-255 "C to give Na,AlH,,
which subsequently breaks up at 275-285 OC, producing A1 and NaH. The
NaH is all decomposed at 425-43O0C. The activation energy for the decomposition of NaAlH, to Na3AlH6 is 40 f 3 kcal m 0 1 - l . ~ Thermogravi~~
metric analysis, d.t.a., and an i.r. study of the reaction of NaOH and
Na,O, with Ga,O, show that NaOH first reacts and a hydroxogallate is
formed, which is transformed into NaGaO, at 130-1 50 "C. At 287-350 "C,
both Na,O, and NaOH attack Ga203,producing NaGaO,. This compound
contains GaO, groups. The d.t.a. method successfully distinguishes the ranges
of maximum reactivity of the two sodium compounds. Above 350C, a
gallate containing GaO, groups is mainly formed in a new reaction of Na,O,.
The reaction of Ga203in the course of the different steps is influenced by its
cryst a1 struct
The enthalpies of reaction of Na,C, and NaHC, with water are used to
evaluate the standard enthalpies of formation at 298 K ; AHi(Na,C,),
4.80 f 0.40; AHy(NaHC,), 23.10 f 0.27 kcal mol-l. The free energy of
~ ~ i.r. spectra of
formation, AGF, of Na,C, is 5.02 f 0.41 kcal m 0 1 - l . ~ The
matrix-isolated NaCN and KCN in the range 33-4000cm-1 have been
examined in Ne, Ar, Kr, and N media. From isotopic frequency shifts for a
13C-enrichedsample of NaCN and 13C- and 15N-enrichedsamples of KCN
it is considered that these two molecules are linear MCN.31g The neutrondiffraction pattern of a single crystal of cubic NaCN has been obtained at
295 K. Combined with earlier results for KCN at 180 and 295 K, these data
are used to determine the distribution of CN- orientations in these crystals,
A monotonic trend appears in the sequence KCN (295 K), KCN (180 K), to
NaCN (295 K), involving a shift in preferential orientation from the [l 113
toward the [loo] directions in the crystal.320The compounds M,Si, (M = Na,
K, Rb, or Cs), Ba,Si,, and K,Ge, contain the ions Sit- and Gei-, which are
tetrahedral. In the K, Rb, and Cs compounds, the F, fundamental of the
316
316
317
318
319
328
G. A. Vorob'ev, V. L. Kubasov, and S. A. Zaretskii, Zhur. neorg. Khim., 1972, 17,

2333.
V. A. Kuznetsov, N. D. Golubeva, and K. N. Semenenko, Dolclady Akad. Nauk
S.S.S.R., 1972,205,589.
M. Viltange, J. Therm. Analysis, 1973, 5 , 101.
G. K. Johnson, E. H. Van Deventer, J. P. Ackerman, W. N. Hubbard, D. Osborne,
and H. E. Flotow, J. Chem. Thermodynamics, 1973, 5 , 57.
Z. K. Ismail, R. H. Hauge, and J. L. Margrave, J . Mol. Spectroscopy, 1973, 45, 304.
J. M. Rowe, D. G . Hinks, D. L. Price, S. Susmann, and J. J. Rush, J . Chem. Phys.,
1973,58,2039.
Elements of Group 1
51
tetrahedron is observed in the far-i.r. absorption spectrum. It is split into two
or three components according to the space group P43n - T:. From the
bands at ca. 345 and ca. 195 cm-l for the ions Sii- and Gei-, respectively, the
force constants ca. 1.05 and ca. 0.87 mdyn A-1 are given to the Si-Si and
Ge-Ge bonds.321The compounds Na,Ge2S6,14H20 and Na,Sn,S6,14H20
are prepared by the reaction of stoicheiometric amounts of Na2S with GeS,
or SnS,. These compounds are isotypic and crystallize in the triclinic system
with space group PI,u = 9.978 and 10.114, b = 7.020 and 7.027, c = 9.601
and 9.801 A, d(expt) = 1.80and 1.97, d(ca1c) = 1.778 and 1.945,respectively;
2 = 1 for both compounds. The compounds contain the ions Ge2St- and
Sn2Si-, which consist of two tetrahedra joined by a common edge. Hexathiodigermanate and distannate represent a new type of inorganic tetrahedral
ion existing in the compounds previously described in the literature as
trithiogermanates, MiGeS,, and trithiostannates, M$3nS3.322The crystallographic parameters of tetragonal Na,SnS4 are a = 7.837, c = 6.950 A, space
group P421C, 2 = 2. The compound consists of discrete SnSi- tetrahedral ions
with Sn-S distances 2.388 A and SSnS bond angles of 107.5 and 113.5".
The Na+ ions are in five-fold co-ordination, with Na-S distances ranging
from 2.789 to 3.094
The co-condensation at 15 K of beams of Nay K, Rb, and Cs atoms with
NO at high dilution in argon produces products which exhibit intense
absorption bands in the i.r. for each metal. The absorptions at 361-219 cm-l
are assigned to the interionic M+-(NO)- vibration and bands at 1358-1374
cm-l are assigned to the intraionic mode (N-0)-. The small effect of M+
on the ( N - 0 ) - mode is explained by the ionic model of polarizable ion pairs.
A large 15Nshift for v2 of the heavy-metal species suggests a bent or linear
Mf(NO)- arrangement, in contrast to the acute triangular Li+(NO)structure,324The structure of sodium trioxodinitrate monohydrate has been
determined by X-ray diffraction methods. The salt Na2N203,H20crystallizes
in the orthorhombic system, group Pbcm, with a = 6.359, b = 9.765,
c = 6.677 A, 2 = 4. The anion (ON202)2-- is planar and the sodium ions
occupy two crystallographically different environments. The Na+ ions at
centres of symmetry have six 0 contacts ranging from 2.35 (to anion 0) to
2.49 A (to OH,), averaging 2.42 A. The Na+ ions on the two-fold axis have
seven 0 contacts in the range 2.51 (to anion 0) to 2.62 A (to OH,) for an
average 2.55 A. The difference in average Na-0 distance for six- and sevenco-ordination corresponds with earlier 0bservations.3~~The gas-phase
reaction between sodium vapour and nitrous oxide has been examined in a
fast-flow, low-pressure reactor using photometric methods. The reaction
rate is 7.6 x 10l1 cm3mol-l s-l at 330 "C, giving an activation energy of
321
a22
a23
324
326
H. Buerger and R. Eujen, 2.anorg. Chem., 1972,394,19.

B. Krebs, S. Pohl, and W. Schiwy, Z . anorg. Chem., 1972, 393,241.
J. C. Jumas, F. Vermot-Gaud-Daniel, and E. Philippot, Crysr. Strucr. Comm., 1973,
2, 157.
D. E.Tevault and L. Andrews, J. Phys. Chern., 1973,77,1646.
H. Hope and M. R. Sequeira, Inorg. Chem., 1973,12,286.
52
Inorganic Chemistry af the Main-group Elements

1.1 kcal mol-1?26 Sodium reacts with red phosphorus to produce Na,P,,.
Alternatively, this compound can be prepared by the thermal decomposition
of Nap,. The compound Na3Pll is orthorhombic, space group Pnab, with
a = 10.410, b = 12.466, c = 9.828 A, 2 = 4. The structure ischaracterized
by discrete P;r groups consisting of eight triple-bonded and three doublebonded P atoms. Sodium ions are five- (trigonal bipyramid, Na-P distances
3.00-3.04 A) and six- (Na-P distances 2.91-3.30 A) co-ordinate in this
structure.327The various compounds and their ranges of homogeneity in the
Na-As system have been confirmed by e.m.f. data from electrochemical
concentration cells using Na as the reference electrode. The standard enthalpies/kcal mol-l and entropies/cal mol-l OC-l of formation of the compounds
Na3As, NaAs, and NaAs, are -51.2, -14.4; -23.0, -5.6; and -25.5,
-4.8, respectively.328The structure of Na4P,Q, at 25 O@ is orthorhombic,
space group P21212,, with a = 9.367, b = 5.390, c = 13.480 A, 2 = 4.
The anion P,04- has a nearly eclipsed configuration. Two of the four Na+
ions are co-ordinated to five Q a t o m while the remainder are co-ordinated to
six 0 atoms. The structure contains chains of cations with four nearly
collinear Na+ per cell parallel to the c-axis. These are surrounded by six
anions. Adjacent anions along the c-axis are separated by a pair of Na+
ions.329
The free energies of formation of a substantial number of sulphides have
been extracted from published data and presented as a function of temperature. The list includes the sulphides Na,S, MgS, and CaS.330Phase-diagram
studies on Na,S-NaOH reveal the compounds Na,S,NaOH, n1.p. congruent
at 875 "C, and Na2$,2NaOH, which melts with decomposition at 675 "C.,,,
In the crystal structure of sodium disulphitomercurate(1r)Na,[Hg(SO3),],H,Q,
the discrete Hg(S0,);- anions are held together by Na+ ions. There are two
independent distorted NaO, octahedra; the 0 atoms belong to five different
SO, groups and to one water molecule. The compound is monoclinic, space
group P2,/n, with a = 8.434, b = 9.345, c = 10.543 A,
= 116.14",
2 = 4.332In sodium silver sulphite dihydrate NaAgS0,,2H20, the Ag atom
is nearly linearly co-ordinated by the S atom and one of the sulphite 0 atoms,
giving a chain-like structure for AgS03. Sodium is octahedrally co-ordinated
by three sulphite 0 atoms and three 0 atoms belonging to water molecules;
the average Na-0 distance is 2.418 A. The unit cell is triclinic, space group
P I , with a = 5.949, b = 9.277, c = 5.465A, a = 101.06", = 90.65",
y = 117.29', and 2 = 2.333Differential thermal analysis of the reactions of
Na,S with As,S, shows that, irrespective of the initial ratio of reagents, the
ca.
326
327
326
329
330
331
332
333
R. E. Walker and J. E. Creeden, Combustion and Flame, 1973,21, 39.

W. Wichelhaus and 1. G. Von Schnering, Nuturwiss., 1973, 60, 104.
L. N. Bludova, G. F. Voronin, and Ya. I. Gerasimov, Zhur.jiz. Khim., 1972,46,2242.
K. V. Jeung and C. Galvo, Canad. J. Chem., 1972,50, 2519.
M. Ancy-Moret, Mem. Sci. Rev. Met., 1973, 70, 429.
E. K. Ovechkin, I. N. Shevtsova, A. E. Voitsekhovskii, L. I. Oboznaya, and L. V.
Kuznetsova, Zhur. neorg. Khim., 1973,18, 1084.
B. Nyberg and I. Cynkier, Acta Chem. Scand., 1972,26,4175.
L. Niinisto and L. 0. Larsson, Actu Cryst., 1973, 29B, 623.
Elements of Group I
53
initial reaction proceeds exothermically at 80-1 30 OC to produce NaAsS,.

This is transformed into N%AsS,, m.p. 50O-52O0C, which is stable up to
800C.334The free energy of formation, AGO, of Na2Te as a function of
temperatureisgivenby AG;/calmol-l = (7.26 f 0.70)(T/K) - (25130 f 350).
The standard enthalpy and entropy of formation are AH; = -23.7 f 0.8
kcal mol-l and AS; = -4.2 f 1.6 cal mol-l, respectively.335
10 Potassium Compounds
Potassium diborate, K,0,2B20, is triclinic, space group P1 , with unit-cell

= 102.75',
parameters a = 6.484, b = 9.604, c = 10.413 A, a = 89.28',
y = 1O1.25Oy 2 = 4. This structure contains a single three-dimensional
borate anion framework composed of mutually linked planar BO, triangles,
diborate groups, and triborate groups in which two of the three B atoms are
tetrahedrally co-ordinated. This combination of groups has not previously
been encountered in a diborate compound. The K+ ions are co-ordinated in an
unsymmetrical fashion by six or eight atoms at distances ranging from 2.631
to 3.106 A.336
KB02,$H,0 belongs to the class of hydroxyl one-ring triborates
and among them represents the first observed tribasic triborate with an
isolated polyion. This consists of two boro-oxygen tetrahedra and a triangle
mutually bound by common apices and forming a triple ring. The polyions
are attached to each other through hydrogen bonds and H 2 0 molecules. The
co-ordination of K+ takes the form of a nonahedron, the apices of which are
OH groups of boro-oxygen tetrahedra, 0 atoms in apices of the triangles,
and water molecules. The compound is orthorhombic, with space group
Pna2,, u = 7.81, b = 13.71, c = 8.80 A,2 = l2.=' Aluminium is resistant
towards molten KOH up to 62OoC. At temperatures above this, reaction
begins which becomes rapid above 800 'C. The reaction leads to the formation of A1203,QK20.Reduction of the melt also occurs since metallic potassium separates, accompanied by the evolution of hydrogenm
The absorption of hydrogen by KC,, at 85.4-123.0 K is reversible. In the
range 0-700 Torr pressure of hydrogen, the amount of hydrogen absorbed
increases with increasing pressure. The limiting H:K ratio of 1.9:1 in KC,,
i s attained only at T < 102 K. The rapid attainment of equilibrium (ca.
10-30 s) and the lack of significant expansion of KC,, on sorption indicate
that the lamellar compound behaves like a molecular sieve with the H2
molecules entering the free interstitial spaces of the host s t r u ~ t u r e Both
.~~
KC, and KC, appear to react preferentially with hydrogen in an H,-D2
M. I. Zhambekov, S. M. Isabaev, A. N. Polukarov, and E. A. Buketov, Trudy. Khim.
Met. Inst., Akad. Nauk Kazakh. S.S.R.,1972,19, 16.
335 V. K. Finogenova, B. A. Popovkin, and G. P. Voronin, Khim. Svyas Poluprou.
Polumetallakh, 1972,348.
336 J. Krogh-Moe, Acta Cryst., 1972,28B,3089.
337 1. Zviedre, J. OZO~S,
and A. Ievins, Lutv. P.S.R. Zinat. Akad. Vestis, Kim. Ser., 1972,
497.
338 V. K.Shcherbakov and S. I. Kumetsov, Zhur. priklad. Khim., 1973, 46,428.
33B P. Lagrange, A. Metrot, and A. Herold, Compt. rend., 1972,275,C, 765.
334
54
gaseous mixture, thus producing a D, enrichment.340The substances KC,
(n = 6.54-9.1) have been prepared from a variety of sources of carbon,
graphitizable and non-graphitizable, and exposed to H, and D2 (1 atm) at
20 "C. The species KH,C, and KD,C, are formed, with x ranging from 9.43
to 0.73. The value of x is marginally greater for H than D. On subsequent
heating to 75 "C, the equilibrium pressure (150-600 Torr) of gas generated
is greater for D, than H, for a given x. KH,C, which is derived from graphitized carbon is semi-crystalline and contains KH in an unusual crystalline
form. KH,C, which is produced from non-graphitized carbon is also semicrystalline but is mixed with free crystalline KH.341
The crystal structures of the azides KN,, RbN,, and CsN, have been
refined on the basis of new X-ray diffraction data. The lattice constants are:
for KN,, a = 6.1129, c = 7.0493 .$; for RbN,, a = 6.3098, c = 7.5188A;
for CsN,, a = 6.5412, c = 8.0908 A. The compounds crystallize tetragonally
with space group I4/mcm and Z = 4. The azide ions are strictly linear and
symmetrical, with N-N bond lengths of 1.16-1.18 A, as shown in Figure
5.342A tracer sectioning technique is used to study the diffusion of K+ ions in
Figure 5 Arrangement of ions in potassium azide, KN,.
single crystals of potassium azide grown from a melt. The cations are the
predominant mobile species and they diffuse by a vacancy mechanism.
The diffusion coefficient over the range 85-354C is given by D =
0.19 exp( -0.80 eVlkT)cm s-l and the enthalpy of migration is 0.80 f
0.06 eV.=, The compound potassium polymetaphosphate (KP03), is insoluble
in water but dissolves in aqueous lithium chloride solutions owing to ion
exchange in which the potassium in the phosphate is substituted by lithium to
produce soluble (Kl-zLizP03)n. The salt is completely soluble when x = 0.5.
a40
341
342
A. Herold, Fr. Demande 2 120 345 (CI. B Old, C Olb), 1972.

C. Gehin and A. Herold, B d . SOC.chim. France, 1972, 3767.
U. Mueller, 2. anorg. Chem., 1972, 392, 159.
J. Sharma and A. L. Laskar, J . Phys. and Chem. Solids, 1973,34,989.
Elements of Group I
55
For x 2 0.5, the mole ratio LiCl:KPO, must be greater than 3 and the concentration of LiCl < 1.2 mol l-1?44 The compound CaKAs0,,8H20 is orthorhombic, with a = 7.146, b = 11.696, c = 7.100 A at 25 OC and 2 = 2,
d(ca1c) = 2.027, d(expt) = 2.10, space group Cm2m. All ions in this compound are completely hydrated, Potassium co-ordinates to eight H 2 0
molecules with K-0 distances varying from 2.756 to 2.960A; calcium
co-ordinates to eight H,O molecules, also with distances Ca-0 of 2.4602.490 A. The co-ordination polyhedron of Ca shares one face of four H20
molecules and two edges with neighbouring co-ordination polyhedra of K.
Each 0 atom of the AsOi- ion is attached by hydrogen bonds to four H20
molecules and forms no bonds with the cations.345The compounds K(SbC1,X)
(X = N,, NCO, or CN) are prepared from SbCl, and KX in liquid SO,. The
reaction of NaN, with SbCl, gave Na(SbCl,N,) contaminated with NaSbC1,.
These compounds are soluble in polar solvents, insoluble in non-polar
solvents, and hydrolyse in H,O. The reaction of KSbC1,NCO with additional
SbCl, gives (SbCl,NCO),; the reaction of KSbCl,N, with BCl, produces
(BCl,N,),. The compounds contain the SbC1,X- ion, which has C,, symrnetr~.~~~
Potassium pentasulphide, K2S5, is triclinic with a = 7.40, b = 13.55,
c = 13.975 A, a = 118"59', p = 85'16', y = 94'45', d(expt) = 2,15,d(calc)
= 2.272 for 2 = 7.%' The crystal structures of K,Rb,,HSO,
(x = 0.330.55) and RbHSO, have been determined by X-ray single-crystal analysis.
&.,,Rb,.,,HSO,
is monoclinic, with space group P2,/c, and has the unit-cell
dimensions a = 7.07, b = 14.10, c = 8.17A, p = 103.9'. All of the Rb+
present is ordered into one of the two sites available to the alkali-metal ions.
The overall structure is composed of closely packed layers of (KzRbl-,HS0,),
which build into a three-dimensional structure intermediate between that of
KHSO, and RbHSO,. The layers are joined to each other by alkali-metal
atom-oxygen bonds. These bonds, which extend out almost normal to the
layers, connect from the K+ and Rb+ ions in one layer to the oxygen atoms in
adjacent layers to complete the co-ordination shells of the alkali-metal ions.
Each K+ and Rb+ ion is bonded to nine 0 atoms. For K+, the bond distances
range from 2.73 to 3.08 A, and for Rbf from 2.87 to 3.24 A. The average
bond distance for the Rb site of 3.04 A is significantlygreater than thatfor the
K site, 2.89 A, and is close to the values found for Rb+ in RbHSO,. This
compound is also monoclinic, space group P2&, with unit-cell dimensions
a = 14.29, b = 4.61, c = 14.76A, /3 = 120.4".348Metal nitrates (M = K
or Ba) react with sulphur trioxide in liquid SO, to form K(N02)S,0,, and
Ba(N0,)2(S,010)2. These compounds contain the NO+ ion. The thermal
decomposition of K(NO,)S,O1, proceeds in two steps, at 135-315 "C and at
944
345
84B
947
34a
M. F. Lu, Hua Hsueh, 1972, 154.

B. Dickens and W. E. Brown, Acta Cryst., 1972,28B, 3056.
U. Mueller, Z . anorg. Chem., 1973, 396, 187.
M. Diot, J. M. Letoffe, M. Prost, and J. Bousquet, Bull. SOC.chim. France, 1972,4490.
W . G. Mumme, Acta Cryst., 1973,29B, 1076.
56
440 O C . Initial decomposition is to K2S20,,S03, and (NO2),S3Olo. Subsequently, K2S20, decomposes to SO, and K2S04.349Crystalline K,CdO,
is prepared by annealing the powder for an extended period at 350-450 "C.
The compound is orthorhombic, space group Pbcn-Dsi, with a = 10.08,
b = 6.18, c = 6.15A, 2 = 4, d(ca1c) = 3.85, d(expt) = 3.6. Although the
space group is different from that of K2Zn0,, there are unmistakable similarities between the two crystal structures.350
11 Rubidium Compounds
Rubidium and caesium gallohydrides, RbGaH, and CsGaH,, can be prepared from the elements at 150-220 O C in the absence of solvents in a sealed
vessel. Attempts to prepare the corresponding sodium and potassium
compounds in a similar fashion were unsuc~essful.~5~
Rubidium silicate, Rb6Si10023,crystallizes with the orthorhombic structure,
space group C2rnm, with a = 9.348, b = 16.290, c = 8.055 A. The structure
consists of a three-dimensional framework of SiO, tetrahedra sharing three
or four corners. The tetrahedra form twelve-sided rings each of which
contains three Rb atoms. At 500 "C an inversion to a hexagonal form having
a = 9.48, c = 8.16 A occurs.352
The Rb-RbOH system has been investigated over the entire composition
range by d.t.a. The complexity of the M-MOH mixtures (M = alkali metal)
decreases down the Group. The Na-NaOH system is complicated by the
reaction of Na with NaOH to produce Na20 and NaH, which dissociates
to give hydrogen. The K-KOH system shows no decomposition of KOH but
features a region of two immiscible liquids which is characteristic of alkali
metal-alkali-metal salt mixtures. Rubidium and rubidium hydroxide form
the simplest system; the components are miscible in all proportions at the
relatively low temperature of 382"C, the melting point of /?-RbOH. The
liquidus decreases continuously from this temperature to the melting point of
pure rubidium, 39 O C . The transition cc-RbOH to B-RbOH occurs at 235 "C,
as can be seen from Figure 6.353
Rubidium trihydrogen selenite RbH3(Se03), is orthorhombic with Q =
5.9192, b = 17.9506, and c = 6.2519 A, space group P21212,. The structure
consists of two types of chains at right angles. One chain is built up of
H,SeO, ions linked by 2.594 A hydrogen bonds and the other of HSe03 ions
linked by 2.571 A hydrogen bonds. The two types of chains are cross-linked
by 2.521 A hydrogen bonds. The Rb+ ion is surrounded by eight 0 atoms
forming a distorted cube, with Rb-0 distances between 2.94 and 3.19 A.354
34Q
350
351
352
353
a54
G. Pevergne, P. Legrand, and J. Heubel, Bull. SOC.chim. France, 1972,4106.

E. Vielhaber and R. Hoppe, 2. anorg. Chem., 1972,392,209.
L. I. Zakharkin, V. V. Gavrilenko, and Yu. Karaksin, Synth. Inorg. Metal-Org. Chem.,
1972, 2, 311.
H. Schichl, H. Voellenkle, and A. Wittmann, Monatsh., 1973, 104, 854.
P. Touzain, Compt. rend., 1973,276, C, 1583.
R. Tellgren, D. Ahmad, and R. Liminga, J. Solid State Chem., 1973, 6 , 250.
57
Elements of Group I
LOO
Rb
20
10
60
80
RbOH
mole % RbOH
Figure 6 The Rb-RbOH phase diagram
The enthalpy of solution of rubidium polytellurites in 20 % hydrochloric acid

has been measured and used to evaluate the enthalpy of formation of the
=
compounds. For Rb2Te205,AH&,8 = -311.5 f 1.3; for Rb2Te4Og,
-463.6 f 1.4; and for Rb2Te40,,3H,0, AH& = -682.3 f 1.6 kcal mol-l.
The enthalpy of formation of Rb2Te,0,,3H20 is - 13.71 f 0.21 kcal r n 0 1 - l . ~ ~ ~
12 Caesium Compounds
The standard enthalpies of formation of the perchloroborates of caesium,

Cs[B(ClO,),], andrubidium, Rb[B(ClO,),], are -188.4 f 1.3 and -184.9 f
1.3 kcal mol-l, respectively. The values are calculated from the enthalpy of
hydrolysis of the perchloroborates in 0.6% NaOH solution and from the
enthalpy of solution of H3BO3, NaCIO,, RbCIO,, and C S C I O , . ~The
~~
enthalpies of solution of caesium nitratoaluminates, Cs[Al(NO,),] and
Cs,[Al(NO,),], in water are -36.53 f 0.16 and -21.27 f 0.14 kcal mol-l,
respectively. The standard enthalpies of formation, AH; of the compounds
are Cs,[Al(NO,),], -351.30 f 0.56, and Cs,[Al(NO,),], -477.81 f 0.67
kcal mol-l, re~pectively.~~
The crystal structures of the orthorhombic and the
high-temperature cubic forms of caesium thiocyanate, CsSCN, have been
investigated by X-ray diffraction, differential calorimetry, and microscopy.
366
V. I. Mazepova, K. K. Samplavskaya, and M. Kh. Karapetyants, Zhur. $2. Khim.,

1973,47, 1052.
N. V. Krivtsov, V. P. Babaeva, and V. Ya. Rosolovskii, Zhur. neorg. Khim., 1 973,18,
367
N. V. Krivtsov, G. N. Shirokova, and V. Ya. Rosolovskii, Zhur. neorg. Khim., 1973,
355
353.
18,958.
58
The orthorhombic phase contains 4 molecules per unit cell, space group
Pnma, a = 7.978, b = 6.332, c = 8.332 A. The structure is layered. In each
unit cell, two Cs+ ions and two SCN- ions lie on planes perpendicular to the
b-axis. Between 197 "C and the melting point of 206 'C, CsSCN crystallizes
in the CsC1-type structure, a = 4.83 A, Z = 1. The symmetry of the cubic
unit cell requires that the SCN- orientation be disordered.358Caesium lead
oxide Cs2Pb0, is prepared as single crystals by annealing Cs,O-PbO,
mixtures (Cs:Pb ratio 2.2: 10) in a silver bomb for extended periods at 600 *C
under argon. The compound is orthorhombic, with space group Cmc2,
and lattice parameters a = 11.3, b = 7.84, c = 6.04 A, Z = 4, d(ca1c) =
6.44, d(expt) = 6.19.359Caesium zinc azide CszZn(N,), is prepared by mixing
aqueous solutions containing CsN, and Zn(N,), in 5:l molar ratio. The
crystals are orthorhombic, a = 6.79, b = 21.98, c = 7.45 A, space group
Dii - P2/b2/c2/m, d(ca1c) = 2.99, d(expt) = 2.98, and Z = 4.360 The
spectra (300-1 800 cm-l) of vapours over dehydrated CsNOz and CsNO,
have been measured at 340-890 "C under argon at 30-50 Torr. At 650750 "C, three bands are found for CsNO,(g) at 790, 1200, and 1460 cm-l
which are assigned to the deformation, symmetric, and antisymmetric
vibrations of the cyclic molecule Cs(O),N. Bands at 1620-1680 cm-l
characteristic for the -0-N=O
group are not observed. At 810-890 "C a
new band is reported at 340 cm-l that is due to the vibrations of the Cs-0
bond. For CsNO,(g) at 650-750 "C the same three bands are found at 790,
1200, and 1460cm-l and, in addition, new bands are observed at 1020
(weak), 1270 (strong), and 1630 cm-l (weak) which are associated with the
/o\
N=O bond. From these data, the ring formula Cs
N=O is proposed.361
\O/
13 Analysis
Sodium ions can be determined potentiometrically by using a Na+-selective

electrode (glass electrode) and Lazaran reference electrode at pH 10 in
ethanolamine hydrochloride buffer, and IS+ can be determined with a K+selective electrode (ion-exchange liquid membrane electrode) at pH 4 - 4 . 5
in a glycine hydrochloride buffer. Na+ and K+ concentrations of ca. 10-1
mol 1-1 can be determined. Li+ and NHZ ions interfere
mol 1-1 to 3 x
in the estimation of K+ ions but Lif, K+, and NH$ ions do not interfere in the
estimation of Na+ ion c~ncentration.,~~
Cyclohexylamine (>0.1 %) can
358
359
360
361
363
S. Manolatos, M. Tillinger, and B. Post, J. Solid State Chem., 1973,7, 31.

P . Panek and R. Hoppe, Z . anorg. Chem., 1972,393, 13.
H. Krischner, H. P. Fritzer, W. Dobramysl, and A. Brunner, 2.Kristallogr., Kristallgeom., Kristallphys., Kristallchem., 1972, 135, 459.
A. Shapovalov, V. F. Shevel'kov, and A. A. Mal'tsev, Vestnik Moskov Univ., Khim.,
1973, 14, 151.
M. Kawamura, H. Shimizu, and T. Kashima, Kyoritsu Yakka Daigaku Kenkyu
Nempo, 1972, 38.
Elements of Group I
59
also be used in combination with the glass electrode at pH >11 to eliminate

the interference of H,O+, especially in the determination of Na+ ion con~entration.,~,The effective cross-sections of Li (and B) n,a reactions are
low but are still sufficiently high to permit their selective determination.
Analysis, which is based on counting the a-particles which are emitted, is
most suitable for thin samples (sample thickness less than the distance of
penetration of cc-particles through the sample.) The minimum amount of Li
which can be determined is 10-8-10-9 g cm-3.364 A neutron-absorption
apparatus for determining Li (or B) consists of a water-filled tank containing
a 241Am-Be neutron source and a BF, proportional counter, the active
portion of which is surrounded by the sample. Sensitivity for Li determination
is 40-50 ~ . p . m . , New
~ ~ 2-hydroxy-2-sulphoazo-compounds have been
synthesized and tested as photometric indicators for the determination of Na.
The most suitable is the potassium salt of 3-methyl-l-phenyl-5-pyrazolone-4azo-l,4-nitrophenyl-2-sulphonicacid. This reacts with Na in a 1 :1 ratio in
various aqueous-organic media in the presence of Bu4NOH to form compounds with molar absorptivity 9.5 x lo3 at 550 nm. Sensitivity is 1 pg Na
(10 ml)-l and Beers law is obeyed for 1-6 pg Na(l0 ml)-1.366Rubidium and
caesium ( 2 4 mg) are determined spectrophotometrically at 350 nm after
precipitation as Rb,Sr [Cu(NO,),] and Cs,Sr [CU(NO,)~],respectively, by
addition of Sr(NO,),, Cu(NO,),, and NaNO,, holding the precipitate at 5 O C
for 3 hours and subsequently redissolving the precipitate in water. The molar
absorptivity is 270 at 350 nm?67 To determine sodium in zeolites by flame
photometry, the metal ion is extracted by ion exchange using AgN0,solution.
The zeolite is finely ground and eluted with AgNO,. When Ag+ appears in
the eluant (test with KCl) the solution is tested for sodium ions. If the
extraction is complete, the AgCl is dissolved by adding KCN and Na+ is
determined flame phot~metricaIly.~~~
Disodium croconate is proposed as
a reagent for the determination of potassium. The technique is based
on the formation of a pale yellow potassium sodium croconate hydrate
which changes colour to bright red on dehydration. The intensity of this red
residue is proportional to the potassium content in the sample. The minimum
determinable K concentration is 0.02 g 1-l; the limiting dilution 1:50 000.
The sensitivity in the determination of K with this reagent is claimed to be
higher than with other known reagents.369An ultramicro-amount of K can be
determined by the isotope-dilution method by using 41K as a spike and a
surface emission mass spectrometer. Isotopic ratios of 41K/39Kcan be measg. The method
ured with an error of 0.25 % and a detection sensitivity of
363
364
365
366
367
368
369
N. V. Electrofact, Neth. Appl. 71 11 344 (CI. G Oh), 1973.

J. Bischof, Z. Dlouhy, V. Kvitek, and M. Vobecky, Jad. Energ., 1972, 18, 296.
F. V. Frazzoli and C. Mancini, Kerntechnik, 1973, 15, 136.
I. S. Markovich, S. L. Zelichenok, N. A. Filyagina, and V. M. Dziomko, Zhur. analit.
Khim., 1973,28,227.
K. Boguslawska and A. Cyganski, Z . analyt. Chem., 1972,261,392.
A. Batca-Cerbu, Chim. Analyt. (Bucharest) 1972,2,214.
0. M. Antoshina, P. Ts. Zilberman, L. P. Adamovich, M. S. Kravchenko, Vim
Kharkiv. Univ., Khim.,1972, 84, 63. (Ref. Zhur., Khim., 1972, Abstr. No. 21G59.)
60
has been applied to the determination of K in deionized water, doubly
distilled water in quartz vessels, and Antarctic snow ice. The average K
concentration in this ice is 4 rJ.gkg-1.370 An amperometric method for the
determination of tetraphenylborate ions has been applied to the determination
of potassium. BPhy is titrated with AgNO, by short-circuit amperometry.
To estimate K+, an excess of NaBPh, is added to a solution of K+ ions at
80 "C to precipitate all K+ as KBPh,. After cooling, NaNO, is added as the
supporting electrolyte together with a surface-active agent such as polyvinylpyrrolidine (0.01 %) to prevent the KBPh, precipitate from reacting with
the titrant, Ag+, with which the excess BPh, is titrated.371Alternatively, the
precipitated KBPh, is filtered off and the excess BPhy ions are estimated by a
chemiluminescencetitration in which a standard solution of lucigen is used
to back-titrate the unused BPh, ions. When all BPhy ionshavebeenconsumed,
a permanent green luminescence is seen in the dark in the presence of NaOH
and I1202.372The isotope dilution method is also used to determine Cs
( < 2 mg ml-l) in the presence of known amounts of K (<50 fold excess).
Saturated potassium solution is added to one of two identical aliquots,
adding 13'Cs solution to both aliquots, extracting the Cs and K in both aliquots in nitrobenzene in the presence of substoicheiometric amounts of
magnesium dipicrylaminate. The counting intensity is measured for both
extracts and the amount of Cs is determined from a calibration graph of
intensity ratio us. Cs:K ratio, which is linear over the Cs:K ratio 1:l to
1:
The development of methods has been studied for the concentration of Cs and Fr from irradiated targets by using extraction and adsorption
chromatography. The methods are based on the use of selective methods of
separating Cs and Fr from other radioactive elements (Ra, Rb, Ac, Ba, U,
and Th) by means of the coprecipitation of Cs+ and Fr+ ions with tungstosilicic acid followed by c h r ~ m a t o g r a p h y . ~ ~ ~
14 Molten Salts
A survey of recent developments in molten salts covers structures, physical

properties, uses, and their reactions.375Spectroscopic techniques for detecting
and identifying complex ions in molten salts are also reviewed, together
with the effects of complex ions on the activity, heats of mixing, and other
physical properties.376The information that can be obtained from Raman and
i.r. spectroscopy is emphasized in a further review of molten salts covering
types of reaction, ion solvation, and interionic vibrations in nitrates, halides,
370
371
37a
373
374
375
376
S. Nakamura, Muroran Kogyo Daigaku Kenkyu Hokoku, 1971,7,443.

S . Ikeda and J. Hirata,Nippon Kagaku Kaishi, 1973, 953.
I. Sarudi, Z . analyt. Chem., 1972,260, 114.
A. V. Pomerantseva and I. E. Zimakov, Zhur. analit. Khim., 1973,28,464.
N. S. Mal'tseva and K. A. Gavrilov, Radiokhimiya, 1972, 14, 773.
J. H. R. Clarke and G. J. Hills, Chem. in Britain, 1973, 9, 12.
M . Terzi, Studii si Cercetari Chirn., 1972, 20, 1049.
Elements of Group I
61
and other salts.377Other topics include thermal ~onductivity,3~~

ultrasonic
velocity measurement~,3~~
and electro~hemistry.~~~
Nitrates.-The solubilities of helium, argon, nitrogen, oxygen, and methane
in equimolar mixtures of NaN0,-KNO, have been determined by a highsensitivity differential micromanometer. The results agree with general
trends valid for weak solute-solvent interactions, i.e. positive heats of
solution and solubilities inversely proportional to the molecular size of the
solute gases. Enthalpies of solution are in the range 16.5-18.5 kJ mol-l at
500-600 K.=l Electromigration of ions in molten LiNO,, NaNO,, and
KNO, has been studied using radioactive isotopes 22Na, 42K, 8sRb, and
13*Csin the form of carbonates. The mobility, u , of the cations at 35OoC
decreases with increasing radius of the molten nitrate cation and decreases
in the order uNa+ < uK+ < URbf < ucS+in LiNO, and in NaNO,. Values Of
u of the cations are equal in KN0,.382The liquidus for the reciprocal system
M,Cs-NO,,NO, becomes simpler with M in the order Li, Na, K, Rb.3S3
The concentration of alkaline-earth metal impurities from a sodium nitrate
melt can be achieved by the method of normal directional crystallization.
The effective distribution coefficients between the liquid phase and NaNO,
are 0.5(Mg), 0.15(Ca), 0.06(Sr), and 0.015(Ba). The concentration effect
increases the sensitivity of the determination of alkaline-earth impurities in
NaN03.3s4Compounds occur in the LiBr-KNO, and NaCl-RbNO, systems.
The former contains LiNO,,KNO, and KN0,,KBr.385 The latter contains
NaN0,,2RbN0,.386 The molten nitrates provide a suitable medium in which
to study an assortment of reactions. Thus the thermodynamics and kinetics
of the reaction:
0, 08,= 20,
can be studied. The absorption is measured of oxygen into a nitrate melt

containing peroxide ions. The equilibrium constant for this reaction at 260 O C
is 2 x
The reaction is exothermic, with an enthalpy change of cu.
-9.90 kcal m01-l.~~The kinetics of the homogeneous-phase oxidation of
D. E. Irish, Ionic Interactions, 1971, 2, 187.
S. Zuca and M. Onisor, Studii si Cercetari Chim., 1972,20,903.
C . Hall and E. Yeager, U.S. Nat. Tech. Inform. Service AD Rept. 1972, No. 749 353.
D. Inman, A. D. Graves, and A. A. Nobile, in Electrochemistry, ed. G. J. Hills,
(Specialist Periodical Reports), The Chemical Society, London, 1972, Vol. 2, p. 61.
881 F. Paniccia and P. G. Zambonin, J. C . S. Faraday I, 1972,68,2083.
382 I. A. Ivanov and V. P. Shvedov, Radiokhimiya, 1972,14,608.
383 P. I. Protsenko and L. S. Grinko, Zhur. neorg. Khim., 1973,18, 230.
384 L. I. Afanasiadi, A. B. Blank, E. S. Solotovitskaya, and E. I. Yakovenko, Zhur.
analit. Khim., 1972, 27, 2345.
386 G. G. Diogenov N N. Nurminskii, and E. A. Anisimova, Trudy. Irkutsk. Politekh.
Inst., 1971, No. 69, p. 119 (Ref. Zhur., Khim., 1972, Abstr. No. llB970.)
386 L. M. Kukis and G. G. Diogenov, Tr. Irkutsk. Politekh. Inst., 1971, No. 66, p. 101.
(Ref. Zhur. Khim., 1971, Abstr. No. 24B1016.)
387 J. M. Schlegel and D. Priore, J . Phys. Chem., 1972, 7 6 , 2841.
377
378
379
380
62
NO- by molecular oxygen according to :

NO-
+ i0, = NO-
in a molten matrix, NaN0,-KNO,, have been studied in the temperature

range 545-690K by following changes in oxygen pressure. Within the
experimental 0 pressure and NO, concentration ranges (80 < Po, < 900
Torr; 0.1 < [NO;] < 0.5 moll-l) the reaction rate is described by the
expression :
-d[NO-]/dt
= k[NO-][O,]
which is consistent with the mechanism:388
NO,
0 2 +NO,
+0
+ 0 +-NO;
NO;
(slow)
(fast)
For the overall reaction:

CzOi-
+ NO, -+
NO,
+ COi- + COZ
in NaN0,-KNO, eutectic at 320-355 "C with flow rates r = 0.06-0.41

min-l of argon bubbled through the melt and for initial K2C03concentrations c = 0 4 . 1 mol I-l, the magnitude of the reaction rate (-d[C,O;-]/
dt = R), at a given temperature and c, decreases with increasing r. Also at a
given temperature and r , the magnitude of R decreases with increasing c. The
mechanism consistent with these observations is :
NO; = NO;
C201-
with
+ NO:
+ 02-
+ 2C02
C0:- = CO, + 02+-
NO,
Equilibrium constant Kl
Rate constant k
Equilibrium constant K2
= kKJ.&)([COz'J [C2O~-I/[CO~-I)
where the concentrations refer to the species in the melt. For the reaction at
255-295 "C in NaN0,-KNO, eutectic containing Cr,O;- and CrOi- in
concentrations much larger than [C,Oi-], the mechanism is:
Cr,02,-
NO:
with
+ NO; = NO: + 2Cr0,2+ Cz0;- 2C02 + NO,

--t
K3
k
(a)
R = kK3[Cr202-][C,O:-l/[CrO:-]
The activation energy for reaction (a) is 18.8 kcal mol-l and k = 0.435 and
1.258 min-l at 255 and 295 "C, respectively.389Using molten NaN0,-KNO,
again, the behaviour of several oxoanions (HSO,, HS03, NO?, Clog, ClO,,
SO",, SO:-) dissolved in this liquid at 300 "C has been investigated using an
0 electrode. Thus NaHSO, and NaHSO, decompose very rapidly, giving
388
389
F. Paniccia and P. G . Zambonin, J. Phys. Chem., 1973, 77, 1810.

R. Vilcu and N. Georgescu, Rev. Houmaine Chim.,1972, 17, 1669.
Elements of Group I
63
S 2 0 i - or S2025- and H20. The ions NO-, SOg-, and SO:- are found to
dissociate to a measurable extent to form 02-.The ions SO:dissociate according to:
and SO$-
+ 02so;- = so, +
SO;- = SO,
and
02-
' comin which SO, and SO, remain solvated in the melt. Although ClO- is
pletely stable in the molten salt, Cloy appears to form an adduct with 02-.
Assuming that the reaction is:
c10,
02-
= clot-
the equilibrium constant is 3.57 x 103.390The Raman spectra of molten

mixtures of KN0,(0-70 mol %) with Ca(N0,),,4H,O at 95-110 "C show
marked variatioiis in the band shapes in regions corresponding to the OH
stretching mode (2850-3850 cm-l) and the v4 NO, mode (700-750 cm-l).
The results are attributed to perturbation of the quasi-lattice of the watersalt melt, in which there may be a displacement of water molecules in the
Molten hydrates
first co-ordination sphere around Ca2+ by the NO,
and molten salt-water mixtures form a link between aqueous electrolyte
solutions and completely ionic melts. Very concentrated aqueous solutions
more closely resemble ionic melts than aqueous solutions. In a study of
AgX (X = C1, Br, or I) in molten Ca(N0,),,4H20 the solubility products of
the silver halides have been determined and
has been calculated for
the process :
AgX = Ag+ + Xin this medium. An analysis of these partial molar entropies of solution
revealed no trend from chloride to iodide, which suggested both the absence
of any polarizable solvent species and that the halide ions have a similar,
namely ionic, environment in the hydrated nitrate. The dissolution process of
AgX in the anhydrous eutectic melts (Li,K)NO, and (Na,K)NO, was similar
but quite different from that in aqueous solution. Molten Ca(N0,),,4H20
behaves, therefore, like an ionic melt and presumably consists of complex
[Ca(H20),I2+ cations and NO3 anions.392 The ternary mixtures AgBrLiNO,, AgBr-RbNO,, and AgBr-CsNO, in the molten and solid states show
a tendency towards immiscibility which increases in the order Cs to Li.393
This trend is reminiscent of that of mixtures of caesium nitrate with alkalimetal nitrites.383The stepwise formation of complexes (AgmIn)(n-n')-in fused
equimolar KN0,-NaNO, at 280 "C has been followed by potentiometric
determination of the free Ag+ ion at different concentrations of NaI KI.
Only mono- and di-nuclear species are present in significant amounts; the
complexes A@,, A@;-, and Ag21t- are proven to exist and some evidence is
300
3B1
3Q2
803
M. Fredericks and R. B. Temple, Austral. J. Chem., 1972, 25, 2319.

K. Balasubrahmanyam and G. J. Janz, J. Solution Chem., 1972, 1, 445.
B. Burrows and S. Noersjamsi, J. Phys. Chem., 1972, 76, 2759.
G. Flor, Atti Soc. Peloritana Sci. Fis. Mat. Natur., 1970, 16, 33.
64
found for the existence of a fourth mononuclear complex, Ag154-.394Association constants of Cd2+with BT to form CdBr+ and CdBr,havebeencalculated
from potentiometrically determined activity coefficients in the molten
solvents 2: 1 KN0,-Ca(NO,), at 200, 240, and 280 "C, and in 2: 1 NaN0,Ca(NO,), at 260C. From these results, the Cd2fBr- pair association
constant is estimated in the hypothetical pure supercooled Ca(NO,), and
compared with theknown association constants in hydrous melts of Ca(NO,),.
The association constant is dependent on the activity of water and indicates
that the equilibrium hydration of Cd2+ involves two water molecules.395In
LiN0,-KNO, eutectic, manganate(v) is stabilized as a blue suspension by
the presence of hydroxide, oxide, and peroxide above a minimum concentration of ca. 0.1 mol 1-1 at 260 "C. Below this concentration, a black manganate(1v) is precipitated. Different results are obtained in Na-K nitrate, where
green soluble manganate(v1) is stabilized by hydroxide and blue soluble
manganate(v) by oxide or peroxide provided the concentration is >0.1
moll-l. Below 0.1 mol 1-1 oxide or hydroxide, mixtures of the two oxidation
states are produced, the proportion being dependent on oxide: Mn ratio.3g6
Halides.-A review on the thermodynamic properties of the vapours of
complex halides from molten salt mixtures includes discussion of experimental techniques such as high-temperature mass spectrometry, the determination of partial pressures, and of the relative ionization cross-sections of
molecules. The results are discussed for binary halide systems of the alkali
metals with Groups IA, 11, 111, IVA, for transition metals, actinides, and
lanthanides, and for reciprocal and similar systems. The molecular structures
and bonding of complex metal halide species are also discussed.397X-Ray
data have been used to determine the number of ions in the first, second, and
third co-ordination spheres of binary salt melts. In NaCl-KCl mixtures,
four cations are distributed about each C1- ion and four C1- ions are distributed about each cation. The second sphere in each case contains nine
ions of the same sign as the central ion. In contrast, LiCl-NaC1, LiCl-KCl,
and LiCl-CaCl, melts are composed of small 16-20 A regions containing a
single salt.389The modes of crystallization of binary molten salts of uni- and
bi-valent metals with a common anion have been summarized from available
data. The boundaries of the phase diagram areas outlining the crystalline
regions appear dependent on the cationic radii and the melting points of
components in the mixture. Using this correlation, the type of crystallization
in systems containing the cations Na+ and Li+ and Na+ and K+ was determined.3ggThe electrical mobilities of ions in mixtures of LiBr-KBr at 350750 "C indicate that the migration velocity of anions remains reasonably
394
395
396
397
398
s80
B. Holmberg, Acta Chem. Scand., 1973, 27, 875.

H. Braunstein, J. Braunstein, A. S. Minano, and R. E. Hagman, Imrg. Chem., 1973,
12, 1407.
B. J. Brough, D. A. Habboush, and D. H. Kerridge, Inorg. Chim. Acta, 1972, 6 , 366.
J. W. Hastie, Ado. Molten Salt Chem., 1971, 1, 225.
N. Ya. Klintsov and I. V. Radchenko, Ukrain.khim. Zhur. (Russ.Edti.), 1973,39,148.
V. I. Zhul'kov, Zhur. obshchei Khim., 1973, 43, 225.
Elements of Group I
65
constant but the cationic mobilities depend strongly on the composition of
the melt. The order of the cationic mobilities is reversed by varying either the
temperature or the composition of the melt. This is attributed to the role
played by different ionic aggregates, including neutral ion pairs, which are
produced in different proportions depending upon which cation is present.40
The electrical conductivity of a salt mixture AX-BY can be successfully
interpolated if this is based on the actual conductivity of the two binary
mixtures AX-BX and AY-BY. The greatest deviation from the interpolated
value arises, however, at the composition of any complex that may be
formed. Thus for CaC1,-KBr, this occurs at KCaX,, and for the KBr-CdCl,
mixture this lies between the compounds KCdX, and KCdX,, where X is
halogen."l The electrical conductivities of BaC1,-MCl mixtures (M = K, Rb,
or Cs) over the temperature range 20-1000 O C show minima which increase
with increasing radius of the alkali-metal cation.402The equivalent electrical
conductivity, A, of molten MF (M = Li, Na, K, Rb, or Cs) at 1290 K has
been measured in a capillary cell constructed from single-crystal magnesium
oxide and platinum electrodes. The trend in A for the series is unique;
usually A for alkali-metal halides decreases in the series from LiX to CsX
instead of increasing. The values are 134.8, 112, 120, 135, and 158.9 i2-l cm2
for LiF to CsF, respectively.403Transport numbers, t , have been determined
from 740 to 78OoC for several melts based on BeF. In binary mixtures
NaF-BeF, and CsF-BeF,, tNa > tcs and the values of t increase logarithmically with increasing concentration of NaF or CsF. In the ternary melt
NaF-CsF-BeF,, tNa < t,, for Cs:Na = 1 :1 . Substitution of NaF by CaF,
leads to a considerable increase in tcB.Beryllium is present in the form of
electrically neutral complexes in the BeF,-based melts and does not contribute
much to the transport of electric ~ h a r g e . 4Evidence
~~
for the presence of the
complex ion Be,F;- comes from Raman spectral data for fluoride melts.
The dimer anion was identified in LiF-NaF-BeF, mixtures by comparing the
melt spectrum with i.r. and Raman spectra of Be2F!- ion in the crystalline
compound Na,LiBe,F,. The species also exists in LiF-BeF, melts at the
appropriate alkali-metal fluoride to BeF, ratio. Increasing the BeF, :MF
ratio causes a progressive increase in the concentration of Be,F:-.405 The
transport number of Na, tNa, is above that in the pure salts for mixtures of
NaCl-NaF and NaBr-NaF?06 The surface tensions of mixtures of MCl-CaCl,
400
401
402
403
404
405
0. P. Mehta, Indian J. Chem., 1973, 11, 351.

B. F. Markov, V. D. Prisyazhnyi, and E. V. Zvagol'skaya, Ukrain. khim. Zhur.
(Russ. Edn.), 1973, 39, 681.
H. H. Emons, G. Braeutigam, and W. Rabe, Z . Chem., 1973,13, 108.
M. V. Smirnov, Yu. A. Shumov, and V. A. Khokhlov, Tr. Inst. Elektrokhim., Ural.
Nauch. Tsenir. Akad. Nauk S.S.S.R., 1972, No. 18 (Ref. Zhur., Khim., 1973, Abstr.
No. 8B1392.)
K. K. Evstrop'ev, I. A. Ivanov, B. S. Kondrat'eva, G. T. Petrovskii, and V. P. Shvedov,
Zhur. priklad. Khim., 1972, 45, 1475.
L. M. Toth, J. 3. Bates, and G. E. Boyd, J. Phys. Chem., 1973, 77, 216.
K. Grjotheim, 0. Haugeroed, H. Stamnes, and H. A. Oeye, Electrochim. Acta, 1972,
17, 1547.
66
and MCl-MgCl, (M = Na or K) have been measured by the pin-detachment
method. The covalent character of molten MgC12 is emphasized. The excess
surface tension is given by the deviation from modifications of the so-called
E. A. Guggenheim equation. In MCl-CaCl, mixtures, the negative deviation
is ascribed to polarization effects and to the enrichment of the surface by the
component with the lowest surface tension. In MCl-MgC1, melts, the
ionization of the partly covalent MgC1,-structure and the formation of
MgCli- complexes are additional factors contributing positive and negative
components, respectively, to the excess surface tensi0n.4~~
The viscosity of
KCl-LiC1, MgC1,-LiCl, and MgCl,-LiCl-KCl melts has been determined
over the entire composition range at 573-914OC. In LiCl-MgCI,, the
viscosity passes through a minimum at 5-10 and breaks at 20 mol % MgCI,.
This behaviour is more distinct at lower temperztures and is taken to confirm
the existence of auto complex ions, e.g. MgC1+. These are also considered
responsible for other physical properties of the system.408The free energy of
mixing of KCl in KCl-MCl, (M = Ca, Sr, or Ba) has been determined by the
cryoscopic method, Negative excess free energies are observed which decrease
as the ionic radius of the alkaline-earth cation decreases.409Mixtures of KBr
with KI at 940-1010 OC behave as a perfect ionic solution according to their
vapour pressures.410
The magnetic susceptibility of solutions of strontium G6.4 mol % in
molten SrCl, has been measured at ca. 900C. The salt becomes less diamagnetic as metal is added. This paramagnetic effect is smaller than expected
for the formation of Sr+ ions according to:
Sr + SrCI, = SrCl
An alternative model is suggested which presumes localized states not
associated with well-defined chemical species.*ll In the equilibrium between
metallic sodium and barium and their chlorides at 100 'C, there is disagreement between the experimental isotherms and that calculated for 2Na(l)
BaCl,(l) = Ba(1) 2NaCl(1). The discrepancy is attributed to the presence
of dimeric molecules Na2, Ba,, and Na&l2 and also to the free energies of
mixing of the metals, of the salts with the metals, and of the salts with one
another. The equilibrium constant which agrees best with experiment is
derived from the equilibrium:
Na,(l)
407
408
409
410
411
+ BaCI,(l) = Ba(1) + Na,CI,(l)
K. Grjotheim, J. L. Holm, B. Lillebuen, and H. A. Oeye, Actu Chem. Scand., 1972,26,

2050.
N. V. Bondarenko, Trudy, Vses. Nauch.-lssled. Proekt. Inst. Alyum., Magnievoi
Elektrodnoi Prom., 1970, NO. 72, p. 104.
I. Adorian and S. Sternberg, Rev. Roumaine Chim., 1972, 17, 1361.
Yu. P. Kubrak and N. L. Yarym-Azaev, 2hur.fiz. Khim., 1973, 47, 1029.
K. Grjotheim, S. Dhabanandana, and J. Krogh-Moe, Acru Chenr. Scand., 1972, 26,
3427.
67
Elements of Group I
The observed equilibrium concentrations correspond to 4-5 atom % Ba

in the metallic phase and ca. 95 mol % BaCl, in the salt phase.412The solubility of aluminium has a minimum in the 1:1 NaCl: AlCl, melt at 0.31 g atom
A1 per mole of AlCl, at 200 "C and increases with increasing temperature. The
metal reacts with the melt to form NaA1C1,.413 The interfacial tension of
molten In and Be in molten chlorides of Na, K, Rb, and Cs has been determined over a wide temperature range by the method of measuring electrocapillary curves. Increasing the radius of the alkali-metal cation and increasing
the temperature both decrease the interfacial t e n ~ i o n . 4A~ ~two-chamber
apparatus has been developed for the determination of hydrogen in molten
salts over wide ranges of temperature and pressure. Illustrative data are
provided for the solubilities of H and He in a LiF-BeF, eutectic melt at
600 O C . 4 1 5 A second apparatus is described which involves displacing dissolved
gas in molten salt by chlorine at 900-930 OC in a quartz beaker and cooling
in this atmosphere. Sample data are provided for CO, in KCl at 1078-1229
and for HCl in NaCl at 1123-1295 K.416The enthalpy of solution of HC1 in
NaC1(1093-1255), KCl( 1062-1 260), RbC1(995-1245), and CsCl(9421218 K) is 2.16, -0.96, -2.23, and -5.00, re~pectively.4~~
The i.r. absorption
spectrum of HCl in fused CaCl,, SrCl,, and MCl (M = Na, K, Rb, or Cs)
shows that monomeric HCl exists in molten SrC1, and CaCl, and that in the
alkali-metal halides the gas is hydrogen-bonded to surface C1- ions.41s The
solubility of C1, in CsCl-LiCl, CsCl-BaCl,, and NaCl-BaCl, at 939-1321 K
and 1 atm is lower than that calculated from the solubilities in the pure salts
and lower than that calculated for a linear change with mixture compositi0n.4~~
At 690-900 OC, the solubility, C , of CO in equimolar KCl-NaCl is (2.785.07) x 10-7molcm-3. The temperature dependence is given by log(C/
mol ~ m - ~=) 1480/4.575(T/K) 1.26 and the solution obeys Henry's law.420
Water vapour reacts with mixtures of MgCl,-LiCl and MgC1,-KCl-LiCl at
700, 750, and 8OO0C and is accompanied by hydrolysis of MgCl,. The
hydrolysis in the melt 10% MgCI2-30% KC1-60% LiCl at 750 "C is more
complete than in the MgCl,-LiCl
For molten NaCl-KCl 1 :1 at
412
413
414
416
416
417
418
410
420
'I1
H. Ostertag, and G. Veisse, Compt. rend., 1973, 276, C, 591.

V. N. Storozhenko, Zhur. j z . Khim., 1972,46,2144.
M. V. Smirnov, V. P. Stepanov, A. F. Sharov, and V. I. Minchenko, Elektrokhimiya,
1972, 8, 994.
A. P. Malinausakas, D. M. Richardson, J. E. Savolainen, and J. H. Shaffer, Ind. and
Eng. Chem. (Fundamentals), 1972, 11, 584.
A. L. Novozhilov, V. N. Devyatkin, and E. L. Gribova, Zhur.jiz. Khim., 1972, 46,
2433.
A. L. Novozhilov, V. N . Devyatkin, and E. I. Gribova, Zhur.jiz. Khim., 1972,46,1856.
L. Novozhilov, E. I. Gribova, and V. N. Devyatkin, Zhur. neorg. Khim., 1972,17,
2078.
M. V. Smirnov, V. E. Kamarov, and Yu. V. Nasonov, Trudy Inst. Elektrokhim. Ural.
Nauch. Tsentr., Akad. Nauk S.S.S.R., 1971, No. 17, p. 45. (Ref. Zhur., Khim., 1972,
Abstr. No. lB1177.)
S. P. Zezyanov and V. A. Il'ichev. Zhur. neorg. Khim., 1972,17, 2541.
L. M. Stukovenkov and Kh. L. Strelets, Trudy. Vses. Nauch.-Issled. Proekt. Inst.
Alyum., Magn. Elektrod. Prom., 1971, No. 79, p. 7 (Ref. Zhur., Met., 1972, Abstr.
No. 56249.)

68
1000-1080 K, the equilibrium constant, 8, = [P(HC1)]2[X(02-)]/[P(H20)],
for
H,O
is given by log ,B2 = 40.78
+ 2C1-
- [55.33 x
= 2HC1+ 02-
103/(T/K)], where the partial pressures,
P,of H,O and HCl in equilibrium with the liquid are fixed by conventional
means and the 0,- mole fraction, X(02-), is measured by electrochemical
means.422
In the phase diagram of KCl with BeC12, two compounds are observed by
d.t.a. These are K,BeCl,, m.p. ca. 550 'C, and KBe,CI,, m.p. 400 'C. Addition
of NaCl to create the ternary mixture KCI-BeC1,-NaCI provides, in addition,
the compound Na,BeC1,.423X-Ray patterns of fused CaCl, have been analysed
and the results used to suggest the number and type of ion in each coordination sphere and also its radius. The successive spheres for CaCl, are
alternately charged.424Thermal analysis, d.t.a., and X-ray diffraction methods
applied to the systems NaC1-MgC1, and KCl-MgC1, reveal two incongruently
melting compounds Na,MgCI, and NaMgC1, in the first mixture and two
analogous incongruently melting compounds K,MgCl4 and KMgCl, in the
second.425The compounds KMgCl, and K,MgCl, are also formed in the
molten fluoridechloride mixture 2K,Mg-2F,2C1.426The enthalpies of fusion
of these compounds and also those of MMgCl, (M = Rb or Cs), Rb,MgCl,,
and Cs2MgC14have been measured and the enthalpies of mixing MgC1, with
KCl, RbCl, and CsCl determined.,,' RbCaC1, is formed in the RbCI-CaCI,
system with a standard enthalpy of formation of -5.29 kcal m 0 1 - l . ~The
~~
phase diagram of the mixture (NaCl),-(RbCl),--BaCl, shows the formation of
BaC12,2RbCl,with a congruent melting point 649 0C.429The existence of the
complexes KF,CaF2, m.p. 1070 "C; KCl,CaCl,, m.p. 754 'C; andCaF,,CaCl,
is established in the quaternary reciprocal system composed of lithium, potassium, and calcium fluorides and chl0rides.4~~
The partial pressures of LiF,
AlF,, LiAlF,, (LiAlF,),, and Li2AlF, in the gas phase over the molten
mixture LiF-AlF, at 946 K have been determined. The enthalpies AH and
entropies A s of the dissociations:
LiAlF4 = LiF AlF,
and
(LiAlF4)2= 2LiA1F4
are determined as AH = 69 f 2, A S = 31.7, and AH = 48.5 f 3.4 kcal

422
423
424
425
426
428
429
430
R. Combes, J. Vedel, and B. TrCmillon, Compt. rend., 1972, 275, C, 199.

A. E. Mordovin, I. F. Nichkov, S. P. Raspopin, and Yu. A. Potemin, Izuest. V . U.Z . ,
Khim. i khim, Tekhnol., 1973, 16, 568.
N. Ya. Klintsov, Ukrain. khim. Zhur., 1972, 38, 759.
K. Grjotheim, J. L. Holm, and M. Roetnes, Acra Chem. Scand., 1972, 26, 3802.
M. A. Kuvakin and Z . M. Novikova, Zhur. neorg. Khim., 1973, 18, 1356.
J. L. Holm, B. J. Holm, B. Rinnan, and F. Groenvold, J. Chem. Thermodynamics,
1973, 5, 97.
B. F. Markov, T. A. Tishura, and A. N. Budarina, Ukrain. Khim. Zhur., 1972,38,823.
N. V. Maksina, L. K. Sosnovskaya, N. A. Finkel'shtein, and N. M. Ryutina, Zhur.
neorg. Khim., 1973, 18, 1098.
E. Ya. Khardikova and V. I. Vereshchagina, Izuest. V. U.Z., Khim. i khim. Tekhnol.,
1972,15, 1875.
Elements of Group I
69
mo1-1, AS = 33.5 entropy units, respectively.431Saturated vapour in equilibrium with CsF-AlF, (0-25 mol % AIF, at 817 K) consists mainly of CsF
and CsF,, while CsAlF, and (CsAlF,), predominate in the gaseous phase at
725 K above 25-100 mol % AIF, m i ~ t u r e s . 4The
~ ~ ternary reciprocal system
LiF-NaF-N~AlF,-Li,AlF, has been studied by thermal analysis, d.t.a.,
quenching, X-ray diffraction, microscopy, and calorimetry. Molten mixtures
can be considered as consisting of the species Li+, Na+, AlFi-, AlF,, and F.
At high fluoride concentrations the dissociation of the AIFk ion to AIF,
and F is negligible. The activity of Na,AlF6 is calculated by treating it as a
part of the ternary reciprocal system 3LiF Na,A1F6 = Li,AlF, 4- 3NaF.
A satisfactory agreement between the Flood, Forland, and Grjotheim (1954)
theory and the experimental values is obtained at dilute Na,A1F6 conc e n t r a t i o n ~X-Ray
. ~ ~ diffraction and d.t.a. measurements show the presence
of a new compound in the NaF-CaAIF, system. This is NaCaAIF,, which
crystallizes in the tetragonal system with a = 7.22 and c = 10.18 A, m.p.
740 0C.434The compound 3BaF2,2AlF, is detected by d.t.a. in the 6Na,3Ba,
2AI-6F system.435The Raman spectra of LiCl-AICI,, KCl-AICI,, and CsCIAlCI, melts in the concentration range 50-100mol % AICI, have been
measured. The melt structures are discussed in terms of the species AlC16,
AI,ClF, Al,CI,, and higher polymers. Their relative stabilities are affected by
the cation, which causes changes in symmetry, force constants, and m a ~ s e s . 4 ~ ~
Equilibrium pressures over the molten mixtures KCl-SbCl,, CsCI-SbCI,,
CsBr-SbBr,, and CsI-SbI, have been measured by a static method using a
glass spoon gauge over the entire composition ranges from 300 to 1OOOK.
The compounds KCI ,SbCI,, 3KC1,2SbCI, ; 3CsCI ,SbCI,, 3CsCl,2SbCl,
(melting incongruently at 560 and 517 OC, respectively); 3CsBr,2SbBr3; and
3CsI,2SbI (melting congruently at 628 "C)are formed in the respective
systems.437-440
The phase diagram of LiCI-BiCl, shows the formation of
LiC1,4BiC13and LiBiCI,, melting congruently at 224 and 210 OC, respectively.
The compound LiC1,4BiC13 decomposes in air and is soluble in mineral
acids and organic s0lvents.4~~
431
432
L. N. Sidorov, E. N. Kolosov, V. A. Davydov, and V. B. Shol'ts, Vestnik Moskov

Univ., Khim, 1973,14, 35.
E. N. Kolosov, T. N. Tuvaeva, L. N. Sidorov, and P. A. Akishin, Zhur.fiz. Khim.,
1973, 47, 1059.
433
434
436
436
437
438
439
44Q
J. L. Holm and B. J. Holm, Thermochim. Acta, 1973, 6 , 375.

H. Pfundt and H. Zimmermann, Erzrnetall, 1972, 25, 564.
M. A. Kuvakin, A. N. Sunin, and L. I. Talanova, Zhur. neorg. Khirn., 1972,17,2785.
E. Rytter, H. A. Oeye, S. J. Cyvin, B. N. Cyvin, and P. Klaeboe, J. Znorg. Nuclear
Chem., 1973,35,1185.
V. G. Zyryanov and E. S. Petrov, Izvest. sibirsk Otdel. Akad. Nauk S.S.S.R.,Ser.
khim. Nauk., 1972,21.
V. G. Zyryanov and E. S. Petrov, Izvest. sibirsk. Otdel. Akad. Nauk S.S.S.R., Ser.
khim. Nauk, 1972, 31.
V. G. Zyryanov and E. S. Petrov, Izuest. sibirsk. Otdel. Akad. Nauk S.S.S.R., Ser.
khim. Nauk., 1973, 9.
E. S . Petrov and V. G. Zyryanov, Izuest. sibirsk. Otdel. Akad. Nauk. S.S.S.R.,Ser.
khim. Nauk., 1973, 8.
N. I. Kaloev and A. K. Tebiev, Zhur. neorg. Khim., 1973,18, 1349.
70
The alkali-metal bromide-MnBr, systems, when studied by d.t.a., reveal

the compounds CsMnBr,, Cs,MnBr,, RbMnBr,, Rb,MnBr,, KMnBr,, and
K,MnBr,, with the 2: 1 compounds existing only at high temperatures. The
structure of MnBr, is changed from the CdI, to the CdCI, type by 20.01 %
LiBr. CsMnBr, and RbMnBr, crystallize with the CsNiCl, type structure,
a = 7.618 and 7.462& c = 6.519 and 6.543& respectively, space group
D&, and 2 = 2. KMnBr, crystallizes with the NH,CdCl, structure, a =
9.185, b = 4.026, c = 15.48 A, space group Dig, and Z = 4. K,MnBr, has
the K,CdCl, type structure, a = 12.68, b = 15.53 A, space group D&, and
2 = 6.442The enthalpies of solution of the compounds CsCl, Cs,MC1,+2
(n = 1, 2, or 3), and MCl, (M = Mn, Fe, Co, Cu, Ni, or Zn) in LiCl-KCl
eutectic have been measured calorimetrically. From these measurements the
enthalpies of formation AHR of the complex solid caesium compounds
shown in Table 9 from the individual salts according to the reaction:
nCsCl(s)
+ MCl,(s) + Cs,MCl,+,(s)
Table 9 Enthalpies of formation of complex caesium compounds

Compound
CsMnC1,
Cs2MnC14
CS,MIlC16
CsFeCl,
Cs,FeCI,
Cs,FeCl,
cscoc1,
cs2coc1,
cs, c oCls
CsNiC1,
Cs,NiCl,
cscuc1,
cs2cuc1,
cs,cuc16
Cs2ZnC1,
Cs,ZnCl,
AH(soln,/kcalmol-1
ANR/kcalmol-l
AH, fus)/kcal mol-l
14.08
12.24
14.31
14.88
14.11
15.90
13.47
16.51
17.77
20.32
15.01
11.25
11.55
14.05
15.90
16.60
-9.86
-6.56
-7.17
-9.78
-7.55
-7.88
-9.56
-11.14
-10.93
-9.37
-1.14
-8.56
-7.40
-8.44
-16.70
-15.97
13.6
9.6
13.1
14.3
11.6
14.2
10.4
10.1
13.1
22.1
15.7
9.6
12.2
are determined. By comparing the relative enthalpies of the above reaction

with the enthalpies of fusion AH(fus)
it is concluded that the co-ordination of
M2f in fused MCl, and in all fused Cs,MCl,+, compounds is tetrahedral.443
The MoC1,-KCl system contains three compounds : K3M0Cl6, congruent
m.p. 873 "C; K,Mo,Cl,, incongruent mop.745 'C; and KMoCl,, forming in
the solid phase at 200 0C.444Only Na3MOC16 and NaMoCI, form in mixtures
442
443
444
H. J. Seifert, Z . anorg. Chem., 1972, 391, 302.

G. N. Papatheodorou, J. Inorg. Nuclear. Chem., 1973,35,465.
E. N. Ryabov, R. A. Sandler, I. J. Kozhina, E. F. Klyuchnikova, and L. P. Dorfman,
Izvesr. V. U.Z., Tsvest. Met., 1973, 16, 125.
Elements of Group I
71
of MoCI, with NaC1.445The phase diagram of BaF,-FeF, is shown to contain

two compounds; Ba,FeF,, m.p. 775 " c , and BaFeF,, congruently melting
at 755 0C?46In the mixtures SrC1,-ThF, and BaC1,-ThF,, only SrCI,, ThF,
and BaCl2,2ThF4form, and these have congruent melting points of 900 f 2
and 980 f 2 "C, re~pectively.4~~
The binary systems RbCI-UF, and CsClUF, have been studied by d.t.a. In the first melt, the compounds 2RbCI,UF,,
3RbCl,UF,, and RbCl,UF, are found. The second system contains the
congruently melting compound ~ C S C I , ~ U F ,Melting
. ~ ~ * diagrams of RbCIUCl, show the presence of four compounds: 2RbCI,UCI,, congruent m.p.
620 "C; 3RbC1,2UC14, incongruent m.p. 430 'C; RbCl,UCI,, incongruently
melts and exists 330-360 OC; and RbC1,3UCI4, incongruent m.p. 345 "C.
The CsCI-UCI, melt contains three compounds: 2CsCI,UCI, congruent m.p.
615 "C, 3CsC1,2UC14, incongruent m.p. 498 "C, and CsCI,UCI,, incongruent
m.p. 375 0C?49Chlorides of lithium, sodium, and potassium form 2MC1,UC14
solids with UC!4.450The phase diagrams of the mixtures MgC12-UF4 and
CaC1,-UF, show the existence of the compounds 3MgC12,2UF4,congruent
m.p. 705 O C , MgCI,,7UF4, congruent m.p. 790 "C, and 2CaC12,UF4,congruent m.p. 635 'C, respectively.451It is suggested that the anionic complex
[PUCI,]~-is formed in MC1,-PuCI, (M = Ca, Sr, or Ba) melts close to the
eutectic composition, and the concentration of this complex ion increases
with increasing ionic radius of M.452D.t.a. and X-ray diffraction measurements on MF-GdF, (M = K, Rb, or Cs) show the existence of three types
of complex fluorides: MGd,F,, dimorphous except KGd2F,, decomposing
peritectically except CsGd,F,, which melts congruently; M2GdF, exists in K
and Rb systems only, decomposing in the solid state; and M,GdF,, dimorphous and congruently melting. a-Rb,GdF, and a-Cs3GdF, are tetragonal
and the /?-forms are cubic. MGd,F, and K,GdF, are paramagnetic, with
deviation from the Curie-Weiss law at low temperat~res.4~~
The CaF2-YF,
and CaF,-NdF, melts have been studied by X-ray diffraction, d.t.a., and
single-crystal growth. One congruently melting compound is observed,
Ca5Y,,F,,, which is hexagonal with a = 11.692, c = 6.964& 2 = 1,
d(ca1c) = 4.607, and d(expt) = 4.560.454Based on the results of d.t.a. and
445
446
447
448
449
450
451
452
453
454
Nguen Ngok Kuan, R. A. Sandler, E. N . Ryabov, I. V. Vasil'kova, I. I. Kozhina, and

E. F. Klyuchnikova, Zhur. neorg. Khim., 1972, 17, 2553.
Ts. G. Tsiklauri, E. G . Ippolitiv, B. M. Zhigarnovskii, and S. V. Petrov, Soobshch.
Akad. Nauk Gruz. S.S.R., 1973, 69, 593.
M. Gudaitis, V. N. Desyatnik, S. P. Raspopin, and I. I. Trifonov, Zhur. neorg. Khim.,
1972,17,2841.
V. N. Desyatnik, S. P. Raspopin, and I. I. Trifonov, Zhur. neorg. Khim., 1972, 17,
2809.
V. N. Desyatnik, S. P. Raspopin, and Yu. F. Chervinskii, Zzvest. V . U.Z . , Tsvest. Met.
1972,15, 120.
V. N. Desyatnik, N. N. Kurbatov, S. P. Raspopin, and Yu. F. Chervinskii, 2hur.fiz.
Khim., 1972, 46, 2159.
V. N. Desyatnik, S. F. Katyshev, S. P. Raspopin, and I. I. Trifonov, Zhur. neorg.
Khim., 1972, 17,2546.
V. N. Desyatnik, S. P. Raspopin, and K. I. Trifonov, 2hur.fi.z. Khim., 1973, 47, 490.
A. De Kozak, M. Samouel, and A. Chretien, Rev. Chirn. mindrale, 1973, 10, 259.
K. Recker and F. Wallrafen, Ber. Deut. keram. Gesellschaft., 1973, 50, 60.
72
X-ray diffraction measurements, the phase diagram of the KF-TbF, system
have been formulated. The formation of five compounds is established, with
KF :TbF, ratios 3 :1 3 :2 , l : 1 , 1:2, and 2 :5. The structures of the compounds
of the composition 1:1 1 :2, and 2: 1 are derived from the CaF, ~tructure.4~~
455
L. R.Batsanova and V. P. Doronina, Izvest. Akad. Nauk S.S.S.R., Neorg. Materialy,

1972, 8, 2142.
Elements of Group II
BY R J. PULHAM
In this Chapter, references which allude to several members of the Group

appear once only under the element first mentioned. The elements of Groups
I1 and I are so closely linked in the field of Molten Salts that, to avoid
duplication, this section appears once only and can be found in Chapter 1.
1 Beryllium
The spectrum of doubly ionized beryllium, (BeIII), has been determined

over the range 500-6200 A. By means of the new measurements and some
previously determined values the term system is recalculated. The ionization
energy of ls2 lS is 1.2 x lo6 f 15 cm-l.l A handbook which includes the
thermodynamics of beryllium and its most important compounds has been
published.2 According to X-ray studies, the phase AlBeo.,B24.2(ca. AlBeB24)
crystallizes just as does tetragonal boron, with space group P4-,/nnmand the
known parameters a = 8.82 and c = 5.08 A. The B atoms are on the same
sites as in tetragonal boron with only small changes of the parameters. The
Be atoms are distributed statistically on B sites that belong to the B12 icosahedra. The A1 atoms are in interstices surrounded by tetrahedra of four
i~osahedra.~
Calculations on the structures of the molecules BeBH, and
BeB2H, indicate that the most stable structure for BeBH, contains an unusual
triple-H bridge. For BeB,H, the structures with a linear arrangement of the
heavy atoms turn out to be of lower energy than those with a triangular
arrangement.4
Beryllium halides and pseudohalides have been reviewed., Non-empirical
LCAO MO SCF calculations are reported for the ground, C,, states of the
Group I1 dihalides BeF2, MgF2,and CaF,. The calculations demonstrate the
importance of 3d orbitals in the bonding of the dihalides and hence in the
a
ti
B. Lofstrand, Phys. Scripta, 1973, 8 , 57.

Ya. I. Gerasimov, A. N. Krestovnikov, and S. I. Gorbov, Chemical Thermodynamics
in Nonferrous Metallurgy: Handbook, Vol. 5 : Thermodynamics of Vanadium,
Mercury, Beryllium, and Their Most Important Compounds, Metallurgiya, Moscow,
1973.
K. Krogmann and H. J. Becher, Z. anorg. Chem., 1972, 392, 197.
R. Ahlrichs, Chem. Phys. Letters, 1973, 19, 174.
N. A. Bell, Adv. Inorg. Chem. Radiochem., 1972, 14, 255.
73
74
determination of the bond angles and bending force constants. For BeF,
and MgF,, d orbitals play an important role in the bonding, but the equilibrium bond angle is predicted to be 180". If contributions from d orbitals are
included in the bonding for CaF, the predicted bond angle is 145", which is in
good agreement with that (141") found in matrix-isolation studies of this
molecule.6 Similar calculations on the low-lying excited states of BeF, amplify
the differences between the valence MO's for covalent and ionic AB,-type
molecules. The lowest energy states in BeF, result from transitions involving
the highest occupied .n,(b,) and .n,(a2)MO's of the ground state to the lowest
unoccupied og(al)MO. This is in contrast to the case of CO, where the
MO's to the rr,(ccl) MO.'
lowest transitions are from the 7rg(b,)and rg(ctz)
The crystal structures of NH,LiBeF, and CsLiBeF, have been determined
by means of X-ray data on single crystals. The Li-F and Be-F tetrahedra
form a three-dimensional network with ideal symmetry Icmm; the actual
structures (space groups Pc2,n and P2,/n) represent two types of deformation
of this framework.* The crystallographic parameters of monoclinic y'Na2BeF4are a = 5.553, b = 8.020, and c = 8.864A, B = 118.36", 2 = 4,
and space group P2,/c. In this structure, one Na atom has seven F neighbours
at < 3.30 A with an average value of 2.406 A. The BeF, tetrahedra are almost
r e g ~ l a r Single
.~
crystals of orthorhombic y-Na,BeF, are obtained from an
aqueous solution of Na,CO, and H,BeF, by heating slowly at a rate of 1 "C
min-l up to 185 f 5 OC, holding at this temperature for 48 h, and cooling
slowly. This high-temperature modification of y-Na2BeF4is monoclinic with
unit cell dimensions a = 5.5590, b = 8.0703, and c = 7.9098 A, B = 99"21',
and 2 = 4.1 Those for the monoclinic compounds Na,Li(BeF,), and
Li2BeF,,H20 are space group P2,/c and P2,, a = 6.522 and 5.430w, b =
9.623 and 4.821 A, c = 9.985 and 7.966& B = 93"12', and 107"12', and
2 = 4 and 2.11 New copper fluoroberyllate complexes have the crystallographic parameters a , b, c, (or a , c), d(expt), 2, d(calc), and space group respectively: orthorhombic [CU(NH,)~]B~F,,H,O,23.942,7.030, and 20.979 A,
1.75, 16, 1.7649, and Pnma or Pn2,a; rhombohedra1 [Cu(en),]BeF4,
8.957 and 9.527A, 1.640, 2, 1.649, and P31c; orthorhombic [Cu(1,2pn),]BeF4,Hz0 (1,2-pn = 1,2-~ropanediamine),14.200, 21.09, and 9.572 A,
(-),
8 , 1.458, and Pccn; orthorhombic [Cu(l ,3-pn)],BeF4,HZO, 11.682,
7.094, and 16.015& (-), 4, 1.573, and Pna2,.12 The d.t.a. curves of the
fluoroberyllates of Cu, Ni, Co, and K show only one endothermic peak at
<150 "C,which is attributed to both fusion and dehydration. Above 150 "C,
the decomposition produces such small enthalpy changes that no further
peaks are 0b~erved.l~
Using H,BeF,, the compounds MHBeF4 (M = K or
J. L. Gole, A. K. Q. Siu and E. F. Hayes, J. Chem. Phys., 1973, 58, 857.
J. L. Gole, J . Chem. Phys., 1973, 58, 869.
a S. J. Chung and Th. Hahn, Muter. Res. Bull., 1972, 7 , 1209.
D. Tranqui, J. Vicat, and S. Aleonard, Cryst. Struct. Comm., 1973, 2 , 339.
lo S. Deganello, J . Amer. Ceram. Soc., 1972, 55, 584.
l1 L. Pontonnier and S. Aleonard, Bull. Soc. franc. Mintfral. Crist., 1972, 95, 507.
l2 J. C.Tedenac, L. Cot, and M. Maurin, Bull. SOC.
franc Mintral. Grist., 1972,95, 525.
l3 T. K. Ghosh and N. N. Ray, J. Indian Chem. SOC.,1973, 50,75.
Elements of Group 11
75
Na), (NO),BeF,, and RH,BeF, (R = PhNH,, pyridine, quinoline, Et,N,

hexamethylenetetramine, or benzidine) can be prepared.14 The thermal
stability of Cs,Be(C104), is similar to that of Rb,Be(C104), but the decomposition of the former is rapid at 270-330C, resulting in Be(CIO,),,
which at 500-660C gives BeO, O,, and Cl,. Rb,Be(ClO,), decomposes at
260-298 "C; the resulting perchlorates break up at 520-580 "C. From X-ray
diffraction data, Cs,Be(C104), and Rb,Be(C10,)4 are cubic with a = 11.67 f
0.01 and 11.38 f 0.01 A, 2 = 4, d(ca1c) = 2.81, and 2.60, and d(expt) =
2.78 and 2.59 re~pective1y.l~
A new nitrosonium chloroberyllate, NOBe2Cl,,
has been characterized. The white solid is isolated in the thermal decomposition of freshly prepared (NO),BeCI, under nitrogen at 140 "C. The
reaction proceeds according to
2(NO),BeCI,
-+
3NOCl
+ NOBe,Cl,
and the compound is characterized by i.r. absorption spectroscopy, chemical

analysis, and X-ray diffraction. At 180"C, the compound decomposes to
give BeC1,.l6
Two of the key compounds in the evaluation and construction of a consistent set of thermodynamic values for beryllium compounds are Be0 and
BeF,. The available measurements on the enthalpies of formation of these
two compounds have been collected and the selected values are AH:,,, for
BeO(c) = -609.6 f 2.5 k3 mol-l and AH;,zss for BeF,(c) = -1026.8 f 3.3
kJ m0l-l.l' For the phase transition a-BeO(c) ---+ B-BeO(c) at Tt = 2107 f
7 "C, the enthalpy change is 56 f 10 cal g-1 for Be0 with purity 99-99.9 %.
Addition of MgO, CaO, SrO, Y203,ZrO,, NiO, AI2O3,SiO,, B,O,, or Thoz
to Be0 does not affect the value of Tt nor the lattice parameters of BeO.
Consequently the Tt value can be used as a d.t.a. temperature standard.18
Mixtures of Be0 with CaO in a 3 :2 mole ratio, pressed to 1000 kg cm-, and
fired at 1300 "C for 2 h followed by melting for 5 min at 1500 "C, produce
dicalcium beryllate, Ca,Be,O,. This compound is identified by its X-ray
diffraction pattern, which is clearly distinguishable from those of the starting
materials.19 The t.g.a. of anhydrous BeSO, under vacuum and in air at
600-815 "C gives an activation energy of 82 kcal mol-l below 640 "C and
one of 48 kcal mol-l above 640 "C for the thermal dissociation of this
compound.20The thermal decompositionof beryllium selenite, BeSe03,4H,0,
proceeds through loss of water at 120 "C and 260 "C followed by recrystallization of the anhydrous compound at 340 "C. At 485-825 "C, decomposition
l4
l5
l6
l7
l9
2o
T. K. Ghosh and N. N. Ray, J. Indian Chem. SOC.,1972,49,925.

L. B. Serezhkina, Z . I. Grigorovich, V. N. Serezhkin, N. S. Tamm, and A. V. Novoselova, Izuest. Akad. Nauk S.S.S.R. Ser. khim., 1973, 451.
J. MacCordick and R. Rohmer, Compt. rend., 1972,275, C, 885.
V. B. Parker, J . Res. Nut. Bur. Stand. Sect. A , 1973, 77, 227.
T. Sata and T. Takashashi, Colloq. internat. Cent. nut. Rech. sci., 1972, No. 205, 331.
I. A. Dmitriev, V. P. Khan, and Yu. M. Kotel'nikov, Isuest. Vyssh. Ucheb. Zaued.,
Khim. khim. Tekhnol., 1972, 15, 1411.
V. G. Vasil'ev and Z . V. Ershova, Zhur. $2. Khim., 1972,46,2958.
16
occurs to produce Be0 and gaseous SeO,. The pressure (p/mm) of the
evolved SeO, changes with temperature according to logp = -1845/T
5.35.,l
Beryllium or BeCI, reacts with N,O,-NOCI mixtures at -4 to 6C
producing monomeric compounds Be(NO,),, Be(N0,),,2N204, and (NO),BeCI, in high yields. The latter compound crystallizes with a cubic lattice in
which a = 14.46 f 0.01 A.z2The standard enthalpy of formation of anhydrous beryllium nitrate, Be(NO,), is - 166.8 f 0.9 kcal mol-l as determined from measurements of the enthalpy of solution of the compound and
of Be(N03),,4H,0 in dimethyl s ~ l p h o x i d eBe(N0,),,4H20
.~~
belongs to the
space group 142d-Dii with a = 11.636 and c = 6.252A, d(ca1c) = 1.60,
and d(expt) = 1.59.24
The linear relation existing between the binding energy of inner electrons, as
determined by p.e. spectroscopy, of the beryllium atom and the charge on the
atom in complexcompounds (acetate, formate, oxide, hydroxide, alkoxide)has
been applied to assess the ability of the ligand to change the effectivecharge on
beryllium. The highest positive charge on Be exists in the acetates.25Beryllium
oxymonohydroxypenta-acetate, [Be,O(AcO),OH], is prepared by the reaction of [B~,O,(ACO)~]
with water in chloroform.26Beryllium dioxydihydroxyocta-acetate, [Be,O,(AcO),(OH),], is prepared from the thermal decomposition of the pyridine complex of Be(Ac0)OH in a stream of dry air at ca.
170C followed by sublimation at 170C under reduced pressure (ca.
5 x lo-, Torr) for 2-3 h. The compound recrystallizes from hot benzene.
The formula is verified by elementary analysis and determination of molecular
weight., Some sterically hindered beryllium alkoxides and their derivatives
have been prepared. The alkoxides [Be(OCMe,Et),], and [Be(OCMeEt,),],
are trimeric in benzene, like the t-butoxide. The dimer has been prepared by a
new route by using lithium 1,l-diethylpropoxide and BeCI,. All three compounds give rise to dimeric alkoxyberyllium chloride-THF complexes. In
addition, [Be(OCMe,Et),], gives [Be,Cl,(OCMe,Et),] with BeCl, in ether.
Beryllium t-butoxide forms no adducts with ammonia, dimethylamine, trior tetra-methylenediamine, or pyridine but 4-(dimethy1amino)pyridine (X)
gives [BeX(OCMe,),]. It forms a compound Me,Be,AI(OBu t)s of unknown
structure with AIMe,. Beryllium 2,6-di-t-butylphenoxide is monomeric in
benzene and is unique in this respect.28 The enthalpies of formation of
z1
22
23
24
25
26
27
M. I. Berezina, V. V. Pechkovskii, and G. F. Pinaev, Zhur. neorg. Khim., 1972, 17,

1795.
L. B. Serezhkina, M. P. Lobacheva, V. N . Serezhkin, N. S. Tamm, and A. V. Novoselova, Zhur. neorg. Khim., 1972, 17, 3191.
P. M. Chukurov, L. N. Peresvetova, S. I. Drakin, and M. K. Karapetyants, Izuest.
Vyssh. Ucheb. Zaved., Khim. khim. Tekhnol., 1973, 16, 145.
B. Ribar, V. Divjakovic, and A. Petrovic, Z . Krist., 1972, 136, 159.
A. I. Grigorev and V. I. Nefedov, Doklady Akad. Nauk S.S.S.R., 1973, 210, 343.
A. I. Grigorev, L. N. Reshetova, and A. V. Novoselova, Zhur. neorg. Khim., 1972,17,
1799.
A. I. Grigorev, L. N. Reshetova, and A. V. Novoselova, Doklady Akad. Nauk
S.S.S.R., 1973, 208, 1356.
R. A. Anderson and G. E. Coates, J.C.S. Dalton, 1972, 2153.
77
crystalline etherates BeC12,AlC1,,3Et20 and BeCl2,2Et2Oare -5 10 f 0.96
and -261.16 f 0.59 kcal mol-l respectively. The enthalpies of solution are:
Be in 4.49N-HCl, -89.61 ; BeC12,2Et20 in 4.45N-HCl, -24.24; and
BeCl,,AlC1,,3Et20 in 4.45N-HCl, -76.16 kcal m01-l.~~
The crystal structure
of triglycine fluoroberyllate in the ferroelectric form is monoclinic with
a = 9.378, b = 12.617, and c = 5.692& ,8 = 110.28', d = 1.641, 2 = 2,
and space group P2,. In the molecule (NH2CH2C0,H),H2BeF4,one glycine
molecule is non-planar but the remaining two glycine molecules are planar
and bound together by a strong hydrogen bond?O An alternative paraelectric phase of this compound exists in which there is position disorder
within the crystal. This is also monoclinic with a = 9.401, b = 12.627, and
c = 5.713& ,8 = 110.13', 2 = 2, d(ca1c) = 1.630, and space group P2,/m.
Transition from the ferroelectric phase causes no significant changes in the
configurations of the glycine molecule^.^^ BeL2 (HL = 2,5-dimethoxy-4chloroacetoacetanilide, o-chloroacetoacetanilide, or m-bromoacetoacetanilide) are prepared by mixing HL with Be(OH), or Be(N03)2,3H20in alcohol.
These bis-(,8-diketonato)beryllium(II) chelates undergo non-destructive
electrophilic substitution reactions such as nitration, bromination, and
~hlorination.,~
N.m.r. and i.r. spectra are reported for Be acetylacetonate,
ethyl acetoacetate, and acetylacetonate-ethyl acetoacetate cornplexe~.~~
Bis(salicyla1doximato)beryllium crystallizes in the monoclinic system with
space group P2,/c, a = 8.79, b = 6.54, and c = 12.64A, = 113', and
2 = 2. From i.r. spectral data, a trans planar structure with an octahedral
configuration around Be is suggested.34Beryllium 3-acyl-2,4-pentanedionates,
BeL (HL = 3-formyl-, 3-acetyl-, or 3-benzoyl-2,4-pentanedione)have been
prepared and characterized by u.v., i.r. and lH n.m.r. spectra. Preferential
chelation to Be through carboxy-groups is found for each ligand.s5 The
formation constants of the chelates of Be2+, Mg2+, and other ions with the
polyhydroxyaromaticligandscatechol, pyrogallol, 2,3-dihydroxynaphthalene,
and protocatechuic acid have been determined at 30C using the IrvingRossotti titration technique. The stabilities of the complexes follow the
Irving-William order in each case and increase in the order Tl+ < Mg2+ <
Cd2+ < Co2+ < Zn2+ < Be2+ < UOi+ < A13+.36
2 Magnesium
The spectrum of triply ionized magnesium (Mg IV) has been studied at
100-2000,3500-3300,710-1130,
and 2470-2535 A. The analysis has been
29
30
31
33
33
34
a6
K. N. Semenenko, S. S. Gavrilova, and A. P. Savchenkova, Zhur. neorg. Khim.,1973,

18, 630.
F. Warkusz and K. Lukaszewicz, Bull. Acnd. polon. Sci., Sbr. Sci. chim., 1973,21,271.
F. Warkusz and K. Lukaszewicz, Bull. Acad. polon. Sci., Sbr. Sci.chim., 1973,21,275.
S . K. Bhasin, P. Umapathy and D. N. Sen, J . Indian Chem. SOC.,1972, 49, 11 13.
L. Maijs. I. Vevere and I. Strauss, Latv. PSR Zinat. Akad. Vestis, Kim. Ser., 1972, 486.
V. K . Sval and P. C. Jain, Indian J. Chem., 1973, 11, 494.
E. Isfan, C. Uncuta, and A. Barabas, Rev. Roumaine Chim., 1973. 18, 1233.
C. R. Jejurkar, I. 0. Mavani, and P. K. Bhattacharya, Indian J. Chem., 1972,10,1190.
78
revised and extended for the 2p44s,5s, 3p,4d, and 5d configurations, and the
2p43s, 4s, 3p, and 3d configurations are now complete. Twenty-eight levels
are established and the configuration is complete except for the 2p4(lS) 4f
level^.^^*^^ The reactions of magnesium with other elements have been
divided into three classes according to the type of compound which is formed.
Thus the elements of the IA and IVA-VIIA groups do not react to any
extent with magnesium and form one class. The elements of the IB, IIB, IIA,
IIIA, and VIIIA groups, including lanthanides, actinides, and carbon form a
second class ; all these elements form compounds, largely intermetallic, with
magnesium regardless of the valence. The third class contains the IVB-VIIB
elements, which form compounds with magnesium consistent with their
formal valence, e.g. Mg2Si.39The intermetallic compound MgBe,, is formed
by quenching or slowly cooling the alloys Al-Be-Mg and Al-Be-Mg-Zn,
which contain up to 2 % of Be. The f.c.c. structure of MgBe,, is confirmed with
a = 10.158 f 0.005 I$.4o The compounds Mg,Sn and MgLi,Sn exist in the
Li-Mg-Sn phase diagram. For Mg,Sn, a = 6.78A.41The valence band of
this compound has been investigated by Auger spectroscopy.42The phase
relationships and crystal structures of magnesium alloys and compounds with
the platinum-group metals have been reviewed. The types of co-ordination
polyhedra and their bonding are discussed.43 The structure of MkGe,Eu
belongs to a new type related to CaF,, AIB,, and Mg2Si,Ce. The cell parameters are a = 4.485, b = 30.60, and c = 4.485 A, Z = 4, and space group
Cmcm. The co-ordination numbers of Mg are 10 or 11 and of Eu 20. The
structure is made up of a wall of trigonal prisms (EuGe8), layers of filled
(MhGeEu,) and empty tetragonal prisms, and layers of filled (GeMg,) and
empty (2MgJ cubes.44A resistometric study of Mg-Cd alloys confirms the
existence of the compounds Mg3Cd, MgCd, and MgCd, but not that of
Mg,Cd,.45
The thermal decomposition of magnesium triborate, MgB60,,,7.5H20
involves loss of six water molecules at 140-200 O C whereas the remaining 1.5
molecules are not lost until 200-450 'C, where complete decomposition
occurs. The formula Mg[B609(OH)2],6.5H20
is more in keeping with these
results. An endothermic process at 690-760 "C is attributed to the reaction
of B203with MgO to form MgB20,, which is one of the final decomposition
37
38
39
40
41
42
43
44
45
G. A. Johannesson, T. Lundstrom, and L. Minnhagen, Phys. Scripta, 1972, 6 , 129.

G. A. Johannesson and T. Lundstrom, Phys. Scripta, 1973, 8, 53.
V. P. Perminov, Metallidy-Str. Suoistua, Primen., 1971, 65 (Ref Zhur., Met., 1972,
Abs. No. 4112).
G. Abdullaev, N . D. Nagorskaya, A. V. Novoselova, and G. N. Ronomi, Vestnik
Moskov. Univ., Khim., 1973, 14, 109.
2. A. Sviderskava, E. M. Padezhnova, and L. S. Guzei, Metalloved. Tsvet. Metal.
Splavov, 1972, 48.
J. Tejeda, N. L. Shevchik, D. W. Langer, and M. Cardona, Phys. Rev. Letters, 1973,
30, 370.
L. Westin, Chem. Comm. Univ. Stockholm, 1972, No. 5 , 35.
0. F. Zmii, E. I. Gladyshevskii, and V. S. Bul'o, Kristallografiya, 1973, 18, 277.
G. Fischer, D. Godel, and S. Steeb, 2.Metallk., 1973, 64, 200.
79
products of the original

The borate, MgB204,is reported as a
novel compound prepared by heating and compressing a molded mixture of
1 : 1 mole ratio B203-Mg0 at 1200-1450 OC and 55-70 kbar for 20-60
min.47
The dissociation energies of the gaseous metal dicarbides, oxides, sulphides,
selenides, and tellurides of the lanthanides and some transition metals
decrease regularly in the order MO > MC, > MS > MSe > MTe for a
given metal M. This empirical correlation is used to calculate the dissociation
energies D;(MC,) to f 10 kcal mol-l or better by extrapolation of the known
D, values for MO, MS, MSe, and MTe for M = Mg, Ca, Sr, Ba, or other
metals, for which experimental data on dicarbides are not yet
The dissociation energieslkcal mol-l for the gaseous molecules are :
MC2
Mg
Ca
Sr
Ba
77
80
87
117
=t 9
f7
f7
f 10
MO
90
87
95
130
MS
67
74
80
95
The published thermodynamic data on carbides have been critically analysed.

Selected material is then used to construct diagrams of the standard free
energy of formation, AG&,, as a function of temperature for Be,C, MgC,,
Mg2C3, CaC,, Na2C2,and other carbides. Selected values for the standard
enthalpy of formation AH,,,/kcal mol-l are Be,C -27.96 f 0.2, MgC,
21.0 f 5.0, Mg2C3 18.0 f 8.0, CaC, -14.2 f 0.4, Na,C, 8.5 f 1.0 (cf.
4.8 f 0.4, Chapter 1). The AGs for these carbides are of the same sign as the
AHS.The AGs of the carbides are generally little affected by temperature, in
contrast to the large changes with temperature of AG for C,H,, CH,, and
C0.49The reaction of magnesium oxide with germanium dioxide at 9901250 OC produces the compounds MgGeO, and Mg2Ge04 simultaneously.
With additives such as V205,MnO,, and Fe203,the reaction occurs at lower
temperatures and the formation of Mg,GeO, is s u p p r e ~ s e d . ~ ~
The crystal parameters of the nitride of magnesium (and that of zinc) have
been determined by neutron diffraction. For Mg3N,, with the antiferrous
manganite structure, a = 9.975 f 0.005A.51 Magnesium halides MgX
(X = C1, Br, or I) and BeCl, react with trimethylsilylazide, Me3SiN3, in
CH,Cl, or Et,O to form magnesium azide and the polymeric compounds
MgXN3, Be(N3),, and ~eCIN30Et2],.1.r. spectra confirm that the covalent
46
47
48
40
61
G. K. Abdullaev, B. S. Abbasov, and P. F. Rza-Zade, Issled. Obl. neorg. $2. Khim.,

1971, 153 (Re$ Zhur., Khim., 1971, Abs. No. 21B880).
H. Hayashi, G. Nishiyama, N. Nakayama, K. Hasegawa, and S. Mizukusa, Jap.
Kokai 73 08, 698 (C1. 15 J2), 1973.
E. E. Filby and L. L. Ames, Inorg. Nuclear Chem. Letters, 1972, 8, 855.
M. F. Ancey-Moret and M. Y. Daniel, Mem. Sci. Rev. Met., 1973, 70, 301.
L. N. Belonogova, V. N. Kryukova, and N. G. Vyazova, Ucheb. Zaved., Khim. khim.
Technol., 1973, 16, 666.
J. Tobisch and W. Hase, Wiss. Z . Tech. Univ. Dresden, 1971, 20, 441.

80
azides of beryllium have a-azido-bridges and that magnesium azides contain
the azide
Magnesium diethyl phosphate Mg[PO,(OEt),], is monoclinic with space
group C2/c, a = 2.214, b = 7.998, and c = 9.300 A, ,tl = 96.82", and 2 = 4.
Each Mg atom is tetrahedrally co-ordinated to four non-ester 0 atoms from
four different diethyl phosphate anions. The angle OMgO, 109.14", is close
to tetrahedral, the Mg-0 distance is 1.091 A, and each magnesium is 4.66 A
from the next. Magnesium is usually found with octahedral co-ordination and
occasionally five- or eight-fold co-ordination. Four-co-ordinate magnesium
is observed in spinel oxides, Grignard reagents, and magnesium halide
etherates. For structures in which magnesium is co-ordinated only to 0
atoms, the Mg-0 bond length increases with increasing co-ordination from
1.91 for four to 2.27A for eight.53 Magnesium hydrogen arsenate heptahydrate, MgHAs0,,7H20, crystallizes in the monoclinic system, space
group C2/c. The unit cell parameters are a = 6.6918, b = 25.744, and c =
11.538& ,tl = 95.15", and 2 = 8. The structure contains two crystallographically independent Mg atoms each co-ordinated to six water molecules; the seventh water molecule is linked by hydrogen bonds only. No
oxygen atoms are shared by co-ordination polyhedra and the crystal structure
can be described in terms of layers parallel to (010) or to (OOl).54
The Auger electron spectrum from a clean magnesium surface has been
investigated under ultra-high-vacuum conditions. The main Auger peaks in
the low-energy spectrum of Mg are assigned to L2,3Y Y transitions. Changes
in the low-energy spectrum occur owing to chemisorption of residual oxygen
in the ultra-high-vacuum system. New larger peaks appear at energies lower
than the original main peaks in the clean spectra for each oxidized surface.
The changes in the spectra are attributed to the shifts of the inner energy
levels and valence band of magnesium on forming bonds to oxygen.55 The
high-resolution spectrum of crystalline MgO(100) has been measured over
the ranges 460-510 and 1088-1 180 eV.56The diffusion coefficient for Mg2+
in MgO at 1000-2400 "C has been determined from concentration gradients
estimated with the aid of mass spectrometry. The problems associated with
the use of the short-lived radioisotope 2sMg are avoided by employing the
stable isotope 26Mgas a tracer. The diffusion coefficient is 4.19 x
cm3 s-l
and the temperature dependence of this coefficient gives an activation energy
of 2.76 f 0.08 eV for cation migration. These parameters are comparable to
those previously reported for impurity ion diffusion. Previous measurements
of cation self-diffusion coefficients obtained with 28Mgare an order of magnitude larger and have been interpreted as intrinsic diffusion. The discrepancy
52
53
54
55
56
N. Wiberg, W. C. Joo, and K. H. Schmid, 2. anorg. Chem., 1972, 394, 197.

F. S. Ezra and R. I. Collin, Acta Cryst., 1973, B29, 1398.
G . Ferraris and M. Franchini-Angela, Acra Cryst., 1973, B29, 286.
M. Suleman and E. B. Pattison, Surface Sci., 1973, 35, 75.
P. J. Bassett, T. E. Gallon, M. Prutton, and J. A. D. Matthew, Surface Sci., 1972, 3 3 ,
213.
Elements of Group I1
81
is attributed to doping introduced by the 28Sidecay product of 28Mg.57The
MgOH radical has been studied by matrix-isolation e.s.r. studies in Ar and
Ne at 4 K . This species is trapped by codeposition of Mg atoms with a
matrix gas containing 1 % H,O,, by codepositing Mg atoms with a matrix
gas and the products of a microwave discharge of H,O vapour, or by passing
the metal atoms, along with H,O vapour, through a tantalum cell at 1700 "C
before quenching in the matrix gas. The molecule MgOH is linear and highly
ionic. Trapped Mgf and probably Mg02H are also observed in the e.s.r.
spectra.58In the study of reactions of gaseous pollutants with solids, the i.r.
spectrum of H,S chemisorbed on MgO and CaO has been measured at 25 'C.
Hydrogen sulphide adsorbed at low pressures forms a layer of hydroxide
ions and a layer of S2- ions. Further reaction leads to the formation of H20
molecules and the conversion of the oxide surface into a sulphide surface;
with MgO, SH- groups are detected. On heating in oxygen the surfaces of
MgO and CaO which have been exposed to H,S, the sulphide layer is oxidized
to sulphite and s ~ l p h a t e . ~ ~
The i.r. spectra and geometry of the Group I1 metal dihalides have been
reviewed. This includes gas-phase and matrix measurements of the i.r.
spectra, isotope effects, matrix effects, methods of determining the stereochemistry, and dimer and polymer species.60The enthalpy of fusion of MgCI,
at the m.p. (980 K) is 9.50 f 0.2 kcal mol-l as determined by high-precision
drop calorimetry.61The i.r. spectra have been determined for MgCl,, Mg,CI4,
and MgBr, trapped in solid Ar at 4-10K. For MgCl,, two bands are
observed at 603 and 585 cm-l which result from different matrix sites. For
MgBr,, an intense band is observed at 490-530 cm-l with three strong bands
at 502, 509, and 520 cm-l and shoulders at 495 and 526 cm-l. The origin of
these multiplets is uncertain. For Mg,CI4, bands are observed at 504, 410,
and 515cm-l. These bands are consistent with an assumed CI-bridged
structure.62 The dehydration temperatures of the alkaline-earth chloride
hydrates increase with decreasing radius of the alkaline-earth ion. Water
molecules are released stoicheiometrically by hydrates of BaCI, and SrCI,
and the dehydration is reversible. Reversibility in the hydrates of MgCI,
and GaCI, is limited. The large activation energy of dehydration of MgCl,
hydrate is explained by simultaneous dehydration and hydroly~is.~~
The
enthalpy changes ( - AH,",,/kcal mol-l) for the reactions
+ MgCl,(s)
2MCl(s) + MgCl,(s)
MCl(s)
and
67
58
69
6o
63
4MMgCl,(s)
3
M,MgCl,(s)
B. J. Wuensch, W. C. Steel, and T. Vasilos, J. Chem. Phys., 1973, 58, 5258.

J. M. Brom and W. Weltner, J. Chem. Phys., 1973, 58, 5322.
M. J. D. Low and P. L. Lee, Water, Air, Soil Pollut., 1973, 2, 75.
I. Eliezer and A. Reger, Coord. Chem. Rev., 1972, 9, 189.
L. Holm and F. Groenvold, Acfu Chem. Scand., 1973,27, 370.
D. L. Cocke, C. A. Chang, and K. A. Gingerich, Appl. Spectroscopy, 1973, 27, 260.
E. Buzagh-Gere, S. Gal, and J. Simon. Proceedings of the 3rd International Conference
on Thermal Analysis, 1971, (publ. 1972), Vol. 2, p. 635.
82
respectively are: M = K , 3.7, and 8 . 5 ; M = Rb, 6.8, and 12.3; M = Cs,

10.0 and 12.0. The AH values are calculated by using published data for the
heats of fusion of the chlorides and the enthalpies of mixing of the liquid
chlorides together with suitable thermochemical cycles.64 The compound
KMgC13,6H20is hexagonal and crystallizes in the space group D&-Pbnn
with lattice constants a = 9.598, b = 16.141, and c = 22.519A, and 2 =
12.65In the reduction of calcium uranium hexafluoride with magnesium, two
steps, with ignition temperatures of 480-530 and 670 f 10C, are distinguished. The ignition temperature of the one-step reduction of CaUF, with
calcium is 840-855 'C. Measurements of the ignition temperature of reactions between Mg and UF, give results scattered between 540 and 760 OC.,,
In a comparison of X-ray photoelectron and X-ray emission spectroscopic
techniques for determining the co-ordination number in compounds of
magnesium (and aluminium), the former technique is preferred. The effect of
changes in co-ordination number (4-6 oxygen ligands) on 2p and 2s ionization energies of magnesium is ca. 10 times greater (ca. 2 ev) than the effect
on the emission energy constant co-ordination number; the binding energy of
the inner magnesium electrons also varies with the nature of the ligand~.~'
The shifts in the lH n.m.r. spectrum of H 2 0 in hydration complexes of Mg2+,
Be2+,AP+, Ga3+, In3+, and Sn4+have been measured at low temperatures.
The shifts are strongly downfield of ethane owing to the electric field of the
cation. The total cationic water shift contains two components, a downfield
contribution from the electric field of the cation and a smaller upfield contribution from solvent structure breaking. These are separately estimated and
previous measurements are shown to be consistent with a hydration number of
six for Mg2+, Ca2+, Sr2+,and Ba2+,four for the alkali-metal ions, and zero
for [Me,N]+. The sulphate anion is also probably tetrahydrated.68Competitive
solvation of Mg2+ in water-acetone solutions has also been followed by
lH n.m.r. In aqueous acetone solutions with H20:Mg ratios of 0-6, complex
spectra are observed for the lH n.m.r. of H 2 0 and acetone down to -95 OC.
The spectra are attributed to competitive solvation where the six-co-ordinate
M2+ solvation shell contains only H20, only acetone, or a mixture of both.
A simple ionic model of these different solvation shells accounts reasonably
well for the observed shifts of H2 0 and acetone protons.69The Mg(CIO,),H20 system has been investigated by Raman spectroscopy. Spectra of solids
ranging from the anhydrous salt to the crystalline hexahydrate are compared
with spectra obtained from simple aqueous solutions of Mg(ClO,), ranging
from dilute to saturated solution and through a series of molten salt hydrates
to the composition Mg(C10,),,2.8H20. The solution and melt data are
analysed in three main composition regions : dilute solution to hexa iydrate,
64
65
66
67
J. Holm, Acta Chem. Scand., 1973, 27, 361.

W. Fischer, Neues Jahrb. Mineral., Monatsh., 1973, 100.
W. Rafalski and B. Syryczynska, Nukleoniku, 1972, 17, 377.
C. J. Nicholls, D. S. Urch, and A. N. L. Kay, J.C.S. Chem. Comm., 1972, 198.
J. W. Akitt, J.C.S. Dalton, 1973, 42.
F. Toma, M. Villemin, and J. M. Thiery, J. Phys. Chem., 1973, 77, 1294.
83
where perturbations of the simple C,, Clog ion spectrum are interpreted as
arising from hydrogen-bonding with H,O ; the hexahydrate region, where
formation of Mg2+-C10; contact ion pairs and continuing C10;-H20
interactions influence the spectrum; and the region of lowest H20 content
and lowest hydration numbers, where quasilattice interactions affect the
spectrum.70 In the Mg(C104)2-NH4C104-H20 system, the salting-out
efficiency of the Mgz+ion is attributed to its strong dehydrating action on the
hydrated NH;
The thermodynamic equilibrium constants for ion
association in aqueous solutions of MgSOa have been determined by electrical
conductivity measurements from 0 to 45 'C. The standard Gibbs energy and
the enthalpy and entropy for the reaction
are calculated from the temperature dependence of the ion-association

constants. For Mg2+-SOi-, AGig8 = -2.91 and AHig8 = 2.04 kcalmol-l
and ASig8 = 16.6 cal deg-l m01-l.~~Magnesium is extracted as Mg(SCN),,4Bu,P04 from solution in aqueous NaSCN by tributyl phosphate. The
extraction increases with increasing NaSCN and Bu,P04 concentrations with
maximum extraction at pH 4.73The i.r. and Raman spectra of solid Me,N
and (CD,),N and the i.r. spectra of MgX,,Me,N (X= C1, Br, or I) and
their perdeuterio-analogues have been measured at -180 "C over the range
40-4000 cm-l. Complexing produces the same type of spectral changes for
Me,N as for ethers. The far4.r. spectra are interpreted in terms of fourco-ordination of Mg and Mg-N-Mg
bridge bonds.74Hexa-aquomagnesium
dihydrogenethylenediaminetetra-acetate, [Mg(OH,),] H,edt a, crystallizes in
the monoclinic space group P2Jc with a = 7.781, b = 13.478, and c =
8.385 A, = 91.55', and 2 = 2. The centrosymmetrical [Mg(H2O),l2+and
[H,edtaI2- species are tied into a three-dimensional network through an
elaborate pattern of hydrogen-bonding. The presence of the N-H bonds in
the [H,edta12- ion leads to amaverage C-N bond length of 1.498A as
compared with 1.471 A in the [H2OMg(edta)l2- chelate. Variations in the
C-C and C-0 bond lengths within these two species are trivial.75Based on
X-ray photoelectron spectra, MgH,edta, Mg,edta, and CaNa,edta have only
unprotonated N in the solid state whereas H4edta and NaH2edta have
protonated N.76 The colourless orthorhombic crystals of magnesium zinc
ethylenediaminetetra-acetate hexahydrate, MgZn(edta),6H20, are elongated
in the c-axis direction and have the parameters a = 14.44, b = 9.76, and
70
D. J. Gardiner, R. B. Girling, and R. E. Hester, J. Phys. Chem., 1973,77, 640.
V. I. Leboshchina, Uch. Zap., Vladimirsk. Gos. Pedagog. Inst., Ser. khim., 1970,22,60.
S . Katayama, Bull. Chem. SOC.Japan, 1973,46, 106.
73
E. D.Kuchkina, F. P. Gorbenko, and G. V. Litvinova, Zhur. analit. Khim., 1973,28,
74
J. Dress and J. Guillermet. J. Chim. phys., 1973,70, 374.

M.O'D. Julian, V. W. Day, and J. L. Hoard, Znorg. Chem., 1973, 12, 1754.
595.
76
76
K.L. Cheng, J. G. Carver, and T. A. Carlson, Inorg. Chem., 1973,12, 1702.
84
c = 13.1 A, 2 = 4, and space group Pna21.77

The crystal structure of the
complex magnesium chloride my-inositol tetrahydrate, MgC12,C,H,01,,
4H20, has been studied as a model for the carbohydratecation association.
This 1 :1 :4complex crystallizes in the monoclinic space group P2Jc with
a = 12.175, b = 7.643, and c = 16.062&
= 96.68', and 2 =4. The
geometry about Mg is not appreciably different from that found in MgC12,6H20. The cation is octahedrally co-ordinated by two cis-vicinal hydroxygroups of inositol and four H 2 0 molecules. The oxygen atoms alone constitute the primary co-ordination sphere of Mg with the distances (& shown
(1). The C1 atoms are 4.673 and 4.759A away from Mg.78Thermodynamic
?H2
-0.
1
'\\
2.094;'
-0'
i2.051
2.032;'
',,2.143
,OH2
,
,#'
MB .
;
'-,2.038
i2079
*#'
'\\
OHz
OH2
(1)
data are reported for eleven nucleotide and phosphate systems: orthoghosphate, pyrophosphate and tripolyphosphate; ribose phosphate; adenosine
5'-monophosphate; and cytidine 5'-mono-, di-, and tri-phosphates. The pKa
values of free acids and stability constants with Mg (and Ni) are reported at
15 O C and ionic strength 0.1. Magnesium behaves similarly with all systems
containing the same number of phosphates which indicates, at the most, a
very weak interaction between Mg and the nucleotide ring in the 1 :1 comp l e x e ~ .The
~ ~ cations Mg2+, Ca2+, and Sr2+ form a series of complexes
containing the anion (dpp) of 1,3-dipheny1-1,3-propanedione,PhCOCH,COPh. These have the formulae and structures shown in Table 1 (2 = 4).
Table 1 Structural parameters of dpp complexes of Group 11 metals

Complex
Mg(dpp)z,2DMF
C a ( d ~ p )4EtOH
~,
S r ( d ~ p ) iMe2C0
~,
Spacegroup
(2)
(3)
(4)
monoclinic
triclinic
triclinic
Complex
M g ( d ~ p ) 2DMF
~,
C a ( d ~ p ) 4EtOH
~,
Sr(dpp),, +Me2C0
77
C2/c
Pi
Pi
Spacegroup
(2)
(3)
(4)
monoclinic
triclinic
triclinic
C2/c
Pi
Pi
alA
b/A
16.893 12.853
15.247 13.555
13.759 14.182
a/"
74.64
107.57
PI"
117.09
95.97
90.36
CIA
16.927
14.097
16.031
yl"
113.59
113.07
A. I. Pozhidaev, N. N. Neronova, T. N. Polynova, M. A. Porai-Koshits, and V. A.

Logvinenko, Zhur. strukt. Khim., 1972, 13, 738.
G. Blank, Acta Cryst., 1973, B29, 1677.
C. M. Frey and J. E. Stuehr, J. Amer. Chem. SOC.,1972,94 8898.
'*
85
Mg
Figure 1 Immediate environment of Mg in the complex Mg(dpp),,2DMF
In (2), each Mg is co-ordinated by a distorted octahedron of 0 atoms, from

two DMF (dimethylformamide) molecules and two p-diketone molecules.
The complex is monomeric and is situated on a two-fold axis with the two
DMF molecules cis to each other (Figure 1). The metal-oxygen distances
fall well within the range usually encountered (2.0-2.15 A), the Mg-O(dpp)
distance (2.057 A) being shorter than the Mg-O(DMF) distance (2.095 A)
as expected from electrostatic interactionsSs0The co-ordination at the metal
is more complex in (3). Complexes (3) and (4) are similar. Co-ordination for
Sr in (4) is shown in Figure 2; all 0 atoms are shown but most C atoms are
Figure 2 Co-ordinationof Sr by oxygen in the complex Sr(dpp)2&Me,CO

F. J. Hollander, D. H. Templeton, and A. Zalkin, Acra Cryst., 1973, B29, 1289.
86
excluded for clarity. Complex (3) consists of a centrosymmetric cluster,
[Ca,(dpp),EtOH],, containing four Ca atoms, two with six 0 neighbours
and two with seven. There are eight 0 atoms which are each shared by two
Ca2+ ions, and these are at the corners of a slightly distorted parallelepiped
in the centre of the complex. Another ten 0 atoms are neighbours of only
one Ca2+each. The Ca-0 distances average 2.37 .$, close to the sum of the
crystal radii (Pauling, 1960), 2.39 A. The range is from 2.256 to 2.508 A.81
The topology of (4)is similar to that of (3) and consists of a centrosymmetric
cluster, [Sr2(dpp)pMe2CO]2,
containing four Sr2+ ions, but the packing is
such that the two compounds are not isomorphous. The contacts of Sr and 0
are as in (3) but the central parallelepiped is more rectangular. The most
acute dihedral angle is 83' whereas in (3) it is 69'. The distances from Sr to
the bridging 0 atoms average 2.55 A with no significant difference between
the two kinds of Sr atom. The distances from the Sr atoms to the unshared 0
atoms average 2.44A, indicating the expected tighter bonding to the unshared
ligands. Where the unshared 0 is that of acetone the Sr-0 distance is 2.60 A,
in keeping with the fact that the acetone is uncharged and thus not as tightly
bound as negative dpp ligands.82A number of new nitrite complexes of the
ligands hexamethylphosphoramide (hmpa) and nonaniethylimidediphosphoramide (nipa) are reported. The complexes have the general formula
[ML,(NO,),] where M = Mg or Ca (and other metals), L = hmpa or nipa,
and x = 1-4. The compounds are characterized and identified by chemical
analysis and physical measurements. With the exception of [M(nipa),](NO,),
(M = Mg or Ca), the nitrite ions are co-ordinated to the cation.83
3 Calcium
The effect of s-d hybridization on the relative stability of the structures of

metallic Ca and Sr has been studied as a function of temperature and pressure
within the context of the pseudopotential theory for metals. The inclusion of
hybridization is found to favour the f.c.c. structure at all pressures and, in
particular, is necessary to explain the observed f.c.c. structure in these metals
at zero temperature and pressure. Phase boundaries are calculated by equating
the free energy of the f.c.c. structure to that of the b.c.c. structure. Temperature-induced phase transitions are predicted to occur at 555 K in Ca and
625 K in Sr as compared with the actual temperatures of 721 and 830 KE4
From the changes in free energy of the reactions of the alkaline-earth
metals with gases as a function of temperature, it is confirmed that at 2981400 K almost all of the residual gases in electrovacuum devices combine
with the metals to form stable compounds.85The dehydration of calcium
81
82
83
84
85
F. J. Hollander, D. H. Templeton, and A. Zalkin, Acta Cryst., 1973, B29, 1295.

F. J. Hollander, D. H. Templeton, and A. Zalkin, Acta Cryst., 1973, B29, 1303.
M. W. G. De Bolster, F. J. Wiegerink, and W. L. Groeneveld,J . Inorg. Nuclear Chem.,
1973, 35, 89.
J. A. Moriarty, Phys. Rev. (B), 1973, 8, 1338.
A. T. Gvil'dis and A. V. Vakhobov, Doklady Akad. Nauk Tadzh. S.S.S.R., 1972, 15,
32.
87
Elements of Group I1
monoborate hexahydrate, Ca[B(OH)4]2,2H20, occurs in two endothermic

steps. In the first stage ( 5120 "C), two molecules of H 2 0 are lost owing to
conversion of the hexahydrate structure into the calcium monoborate
tetrahydrate structure. In the second stage (120-520), the Ca[B(OH),],
structure is completely decomposed into a mixture of CaO and B203.These subsequently recombine exothermically forming calcium metaborate.86Calcium
pentahydroborate CaB204,5H20(= Ca [B2O(OH),],2H2O) forms triclinic
crystals with a = 7.875, b = 6.534, and c = 8.104A, a = 111"32', B =
111"20', y = 72"42', d(expt) = 2.00, and d(ca1c) = 2.02 for Z = 2. The
Ca2+ion is seven-co-ordinated by 0 atoms of OH groups, with bond lengths
2.37-2.57 A, and an eighth OH group is at 3.58 A.87Single-crystal X-ray
diffraction data show that johachidolite possesses the formula CaAI(B,O,).
The topology of the structure leads to an atomic arrangement of unusually
high density (3.44) for this composition. With respect to co-ordination by
oxygen atoms, B is tetrahedral, A1 is octahedral, and Ca occupies a distorted
pentagonal antiprism. The polyhedral interatomic distances reveal severe
cation-cation repulsion as a consequence of edge-sharing by the highly
charged polyhedra. Because the bond strengths are fairly evenly distributed
the compound possesses no good cleavages. The highly charged cations in the
small polyhedra are responsible for the hardness (6.5-7 on the Mohr scale).88
Crystals of calcium bromoborate, Ca2B,0,Br, have pseudotetragonal
orthorhombic symmetry, a = 11.397, b = 11.255, and c = 6.293 A, space
group Pnn2, and 2 = 4. The structure consists of chains of corner-sharing
BO, tetrahedra which run in the z direction. These are linked in the x and y
directions by B atoms which occupy the centres of triangles of 0 atoms. The
Ca and Br ions are located in tunnels which exist in the three-dimensional
structure so formed.89Calcium or strontium hydride reacts with AlH, in
tetrahydrofuran to form Ca(or Sr) AlH,,THF. In ether, Sr(AlEt,), reacts
with LiAIH, to give a mixture of hydrides and hydride complexes of Sr and
Al; with excess LiAIH,, SrHAIH, is produced. A similar reaction with
Ba(A1Et4), gives Ba(AlEt,)(AlH4). The pyrolysis of Sr(AlH4), in THF-MePh
results in disproportionation to Sr,(AlH,), and AlH,.'' Calcium gallium
nitride is a metallic electronic conductor and can be prepared by the reactions
+ 3GaN 3CaGaN + N2
Ca + GaN +CaGaN
Ca,N2 4- 3Ga + i N 2a3CaGaN
Ca,N2
86
G. K. Abdullaev and Kh. R. Samedov, Issled. Obl. neorg. fiz. Khim., 1971, 160,
(Ref. Zhur., Khim.,1971, Abs. NO. 21B897).
Yu. K. Egorov-Trismenko, Yu. M. Baryshnikov, D. P. Shashkin, M. A. Simonov,
and N. V. Belov, Doklady Akad. Naulc S.S.S.R., 1973, 208, 1082.
P. B. Moore and T. Araki, Nature Phys. Sci., 1972, 240, 63.
D. J. Lloyd, A. Levasseur, and C. Fouassier, J , Solid Slate Chem., 1973, 6 , 179.
V. V. Gavrilenko, Yu. N. Karaksin, and L. I. Zakharkin, Zhur. obshchei Khim., 1972,
42,1564.
88

The crystallographic parameters of the tetragonal compound are a = 3.570
and c = 7.558 A, space group P4/nmm, d(expt) = 4.29, and d(ca1c) = 4.268
for Z = Zgl Calcium oxogallate is prepared as single crystals from CaOGa203melts. The space group is C&-Pna2, with a = 10.189, b = 7.725, and
c = 9.032A. The co-ordination of Ca2+ by 0 is irregular but Ga3+ is tetrahedrally co-ordinated by 0.92
The compound Ca3Si30,,H,0 (rosenhahnite) belongs to the triclinic
system with 2 = 2. On thermal dehydration the H20 molecule is slowly
released at 4O0-50O0C and the single crystal transforms into an almost
perfect single crystal of CaSiO, (wollastonite), which is known to contain
infinite Si30gchains. The transformation is irreversible. The structure of the
original material shows distinct linear (but kinked) groups of three SiO,
tetrahedra, the two outer Si atoms each sharing a common 0 with the central
Si. There is no sign of any separate H,O molecule. One of the three terminal
0's at each end of the group has a significantly longer bond to Si than the
other two and has significant bonding to only one Ca, as against two or three
for the others. The groups of three SiO, tetrahedra must be Si,O,(OH),. The
dehydration process consists of the polymerization of these groups into
infinite Si,Og chains, each join producing a water molecule, and local rearrangements giving channels through which these molecules can diffuse.93
The electrical conductivity of solutions of calcium in liquid ammonia varies
with time, remaining relatively constant immediately after dissolution, then
dropping to a limiting and constant value after ca. 1 h. This behaviour
is ascribed to initial electron solvation followed by gradual formation of
Ca(NH3), and subsequent reaction of Ca with NH; ions.94On heating the
nitrides M3N, in dry, oxygen-free hydrogen at ca. 600 O C (M = Ba) or
700-8OO0C (M = Ca) the compounds M,NH are produced. The metal
hydride nitrides have a cubic NaCl structure with Q = 10.13A, d(expt) =
2.45, and d(ca1c) = 2.44 for 2 = 16 in the case of Ca, where N and H atoms
are ordered on the anion sites. For Ba, u = 5.86A, d(expt) = 4.75, and
d(ca1c) = 4.77 for 2 = 2, with a statistical non-ordered distribution of N
and H on the anion sites.95The compounds Ca,PI and Ca,AsI are prepared
from the elements at 700-750 'C. They have a rhombohedra1 structure and
are easily h y d r ~ l y s e dAlkaline-earth
.~~
pnictides crystallize with the Na,O,type structure, characterized by P, or As, groups. Crystallographic parameters are (MX, a, c/A) Cap, 7.632, 5.731 ; SrP, 8.040, 6.031 ; CaAs, 7.858,
5.921; and SrAs, 8.269, 6.201. The corresponding phases BaP and BaAs
have not been found.97
91
g2
93
94
g5
96
97
P. Verdier, R. Marchand, and J. Lang. Compt. rend., 1973, 276, C, 607.

13. J. Dieseroth and H. Mueller-Buschbaum,Z . anorg. Chem., 1973, 396, 157.
J. W. Jeffery and P. F. Lindley, Nature, 1973, 241,42.
V. N. Epimakhov, M. M. Tarnorutskii, Yu. M. Mishenov, and N. B. Kolosova,
Zhnr. obshchei Khim., 1973, 43, 499.
J. F. Brice, J. P. Motte, and J. Aubry, Compt. rend., 1973, 276, C , 1093.
C . Hamon, R. Marchand, and J. Lang, Compf.rend., 1972, 257, C, 1511.
A. Iandelli and E. Franceschi, J . Less-Common Metals, 1973, 30, 211.
89
A method has been developed to identify species responsible for the emission in visible alkaline-earth bands in flames. This is based on measurement
of the ratio of band to atomic line intensity for a given element in two flames
of the same temperature but with a different, known gas composition. In
C,H,-air, H,-air, and moist CO-N,-0, and CO-N,O flames, the Ca bands
at 5540,6020, and 6230 A, and the Sr bands at 6060,6470,6690, and 6820 A
are due to the monohydroxide, MOH, whereas in the C2H2-air flame the
Ba bands at 4870 and 5120A are due to both oxide and monohydro~ide.~~
At constant ionic strength (0.5M)the pH ranges at which metal hydroxides
precipitate are Ca(OH), > 11.5, Zn(OH), > 5.8, Sr(OH), > 10.8, Al(OH),
4.2-12, and Fe(OH), > 6. The minimum solubilities (in mol 1-l) of the
hydroxides are Ca(OH),, 1.8 x
Zn(OH),, 0.25 x
Sr(OH),,
4.3 x
Al(OH),, 0.20 x
and Fe(OH),, 1.5 x lop5. Maximum
precipitation of Ca(OH),, Sr(OH)2, and Zn(OH), occurs at pH > 13; of
Al(OH), at pH 6-9.5; and of Fe(OH), at pH 6.5-12.99 Solutions of CaySr,
or Ba in liquid ammonia at -78 to -33 "C react with H,S in excess to form
the metal sulphide. Degassing at 700-800 O C under reduced pressure gives
the respective metal sulphide in a pure form. The lattice constant, a, of the
cubic compounds is CaS, 5.696; SrS, 6.020; and Bas, 6.388 A. These values
are in very good agreement with those reported previously.looAn alternative
high-temperature preparation is achieved by passing a stream of dry hydrogen
through a layer of alkaline-earth metal sulphate. For Ca the reduction
temperature is > 850 OC and for Sr and Ba > 950 'C.The products contain
ca. 98 % MS.lol A new family of sulphur compounds of the melilite type has
been prepared containing Ca or Sr. Two kinds of compound belong to this
family; the compounds L3a3,Ga,S14 (L = La or Ce) and the compounds
MLaGa3S, and MLaAl,S, (M = Cay Sr, or Ed1). In these compounds,
M and L cations occupy the same seven-co-ordinate crystal sites and A1 or
Ga cations are tetrahedrally co-ordinated with S.lo2
The crystal structure of CaC12,4H20 is triclinic, space group Pi, with
a = 6.593,b = 6.364,andc = 8.557& a = 97.77O,P = 93.52', y = 110.56'
and Z = 2. The two chloride ions and four water molecules form a trigonal
prism about the Ca2+ ion (Figure 3; bond lengths/&. Of the three geometrical isomers that can be proposed for a trigonal prism composed of two
chloride ions and four oxygen atoms, the one found has the two chloride ions
at maximum separation. Of the three forms of crystalline CaC1,,4H20 which
are known to exist, this is the a-form; this appears the stable form and, under
the appropriate conditions, the other crystalline modifications convert into
this form.lo3 The interaction of sucrose (L) with alkaline-earth metal (MJ
Qs J. Van der Hurk, Tj. Hollander, and C. Th. J. Alkemade, J. Quanr. Spectroscopy
Radiative Transfer, 1973, 13, 273.

L. A. Zhukova, V. S. Chikov, and V. V. Rachinskii, Kolloid. Zhur., 1973, 35, 158.
looT. Petzel, 2. anorg. Chem., 1973, 396, 173.
lol E. Pedak, M. Allsalu, and M. Kanter, Zhur. priklad. Khim., 1972, 45, 2619.
lo2 A. M. Lozac'h, M. Guittard, and J. Flahaut, Muter. Res. Bull., 1973, 8 , 75.
lo3 U. Thewalt and C. E. Bugg, Acta Cryst., 1973, B29, 615.
99
90
Ca-0 (1)
Ca-0(2)
Ca-0(3)
Ca-0(4)
Ca-Cl(1)
Ca-CI (2)
2.468
2.384
2.352
2.461
2.853
2.842
Figure 3 Co-ordination of Ca in CaC1,,4H2O

chlorides has been followed by potentiometric titrations. The formation of
complexes in solution is indicated at (MC12),L,, where x , y = 1, 2, or 3. The
complex-forming capacity decreases in the order Ba2+ > Sr2+ > Ca2+ >
Mg2+.lo4The crystal structure of a hydrated calcium bromide salt of lactoacid ( 5 ) , has been determined by
bionic acid, 4-(~-~-ga~actosido)-D-g~uconic
X-ray diffractometry. The salt is orthorhombic, space group P212,2,, with
6
OH
H02C-CH-CH-CH-CH-COO1
OH 0
Galactose
OH
Ca2+ Br-
t5 )
a = 16.662, b = 15.075, and c = 8.255 A. There are four CaBr,4H20,C12H2,O,, formula units in the unit cell. Lactobionic acid, which is derived by
oxidation of the glucose unit of lactose, contains a galactose moiety and a
gluconic acid residue. Like the anions of other hydroxycarboxylic acids, the
gluconate ion binds calcium in aqueous solution. In this crystalline complex,
the lactobionate ions are also co-ordinated to the calcium ions through their
gluconate residues, with no direct calcium-galactose interactions. Ca2+ is
surrounded by a shell of 0 atoms, and the Br- ion is hydrogen-bonded to
H 2 0 molecules and to OH groups (Figure 4). The closest Ca-Br contact is
4.78 A, a distance 1.75 A longer than the sum of their ionic radii. The Ca2+
ion is co-ordinated to three H20 molecules (W,, W,, and W, at Ca-0
distances 2.451,2.368, and 2.430 A respectively) and to the gluconate moieties
of two lactobionate ions. One binds to the Ca2+ion through atoms O(C-1)
2.456, O(2)2.480, and O(3) 2.524& and the other binds through atoms
lo4 A.
J. Dangre, J. Univ. Poona, Sci. Technol., 1972, No. 42, 123.
91
0 (3)
Figure 4 Co-ordination of Ca by oxygen in the calcium bromide salt of lactobionic acid

O(5)2.507 and O(6) 2.425 A. The Ca2+is thus surrounded by eight 0 atoms
which assume a distorted square-antiprism arrangement, uiz. three 0 from
H 2 0 molecules, four 0 from OH groups, and one from a carboxy-group.lo5
itself, which does
With lactose (4-O-/3-~-galactopyranosyl-~-glucopyranose)
not contain a carboxy-group but consists of two cyclic sugar moieties, galactose and glucose, Ca2+bonds to the hydroxy-groups of both rings. This is an
outstanding feature of the crystal structure of the hydrated calcium bromide
complex with lactose, CaBr2,7H20,C12H220,1,which is orthorhombic, space
group P21212,, with a = 21.952, b = 13.705, and c = 8.792A, d(ca1c) =
1.678, d(expt) = 1.68, and 2 = 4. The Ca2+ion is co-ordinated by the 0 of
two lactose molecules and four water molecules; one lactose molecule is
co-ordinated through two of the OH groups in its galactose moiety, and the
second is co-ordinated to two of the OH groups in the glucose moiety. As
before the calcium ion is surrounded by a shell composed of eight 0 atoms.
These form a very distorted square antiprism with Ca-0 distances ranging
from 2.379 to 2.538 A. There are no hydrogen-bonds between 0 atoms within
this shell. There are no close contacts between Ca2+and Br- ions; the closest
Ca-Br distance is 4.94 A, a distance 2 A longer than the sum of the individual
ionic radii. The Br- ions are hydrogen-bonded to H20 molecules and to OH
groups.lo6The calcium chloride heptahydrate complex with lactose is almost
isostructural with the preceding compound. CaC12,7H20,C12H220,1is
lo5
Io6
W. J. Cook and C.E. Bugg, Acta Cryst., 1973, B29,215.

C. E. Bugg, J. Amer. Chem. SOC.,1973, 95,908.

92
orthorhombic, space group P2,2,2,, with a = 21.562, b = 13.455, and c =
8.792 A, and 2 = 4.17 Crystalline Ca12,7DMF, Sr12,2DMF, Sr12,8DMF,
and Ba12,8DMF are prepared by cooling the saturated solutions of the
corresponding iodides in DMF. The i.r. carbonyl stretching frequency of
DMF is reduced by 10-35 cm-l on complexing, which indicates that coordination to the metal is through the 0 atoms of the ligand. Ca12,7DMF
melts at 88 OC, loses all DMF with partial decomposition of CaI, at 321 'C,
and completely decomposes at 463 "C. A11 the compounds decompose in the
atmosphere.losThe i.r. spectrum (65-4000 cm-l) of CaCr0,,4CO(NH2), is
compatible with CO(NH2), molecules bonded to Ca2+ through 0 and to
[Cr0,J2- through H atoms of the NH group.loSCalcium oxydiacetate (oda)
hexahydrate, Ca [O,CCH,OCH,CO,] ,6H,O crystallizes in the monoclinic
space group P2Ja with a = 12.830, b = 15.915, and c = 6.185&
=
118.03O, and 2 = 4. The Btructure consists of Ca(oda),5H20 complexes
linked only by hydrogen-I%-nding to the sixth H20 molecule. The Ca2+
co-ordination is eight-fold, consisting of 0 atoms from five H 2 0 molecules
and two carboxylate groups and the ether oxygen of the terdentate oda ligand.
The Ca-0 distances range from 2.375 to 2.549A. That the ether 0 of the
ligand plays an important part in the Ca2+co-ordination is shown by a short
calcium-ether oxygen separation of 2.43 1 A compared with the slightly
longer calcium-carboxylate oxygen separations, 2.472 and 2.446 A. The
observed irregular eight-fold co-ordination is not unusual for Ca2+ complexes.ll0 The compound Ca(MeC0,)(MeCOS),3H20 is monoclinic, space
group P2,/c, with a = 6.75, b = 15.44, and c = 11.34L$, @ = 113O14',
d(expt) = 1.44, and d(ca1c) = 1.40 for 2 = 4.ll1
4 Strontium
The spectrum of doubly ionized strontium (SrIII) emitted from a sliding spark
discharge has been studied. About 590 SrIIIlines are identifiedin the 9800-350
A range, all but eight of them being previously unobserved. Seventy-oneeven
and seventy-six odd energy levels are established, including all levels of the
4 ~ 5 8 ,68, and 6h configurations.l12 Strontium chloride reacts with NaBH4
in THF to produce Sr(BH4),,2THF. When this is heated at 180-190C,
strontium tetrahydroborate is obtained and this is stable up to 410-420 "C.
The compound is soluble in the organic solvents THF, diglyme, dioxan, and
et her.l13 Distrontium boroaluminate, 2Sr0 ,A1,03,B203 has space group
Io8
W.J. Cook and C. E. Bugg, Actu Cryst., 1973, B29, 907.

E.Ya. Gorenbein, V. V. Skopenko, and T. D. Zaika, Zhur. neorg. Khim., 1973,18,54.
lo9
A . M. Slobodchikov and N. N. Runov, Uch. Zap., Yaroslau. Gos. Pedagog. Inst.,
111
1972, No. 103, p. 93.

V. A . Uchtman and R. P. Oertel, J. Amer. Chenr. SOC.,1973, 95, 1802.
M. M.Bore1 and M. A. Ledesert, Compt. rend., 1972, 275, C, 183.
W.Persson and S. Valind, Phys. Scripta 1972, 5, 187.
V. I. Mikheeva and L. N. Tolmacheva, Zhur. neorg. Khim., 1973, 18, 1703.
lo7
112
113
93
Di:-Pccn with a = 15.17, b = 8.86, and c = 5.48 A, and Z = 4. The structure consists of chains parallel to the c-axis which are built up of AIO, tetrahedra and BO, triangles. The basic unit of these chains is a six-membered
ring which consists of two A10, tetrahedra and a B 0 3 triangle. This sixmembered ring is a new kind of complex polyanion. The Sr atoms serve to
hold the chains together through co-ordination to 0. Each Sr is surrounded
by eight 0 atoms.l14Small single crystals of a new strontium indate, Sr,In,O,,
are prepared by heating 2 :1 SrO-In,O,mixtures above 2000"C.Thecompound
crystallizes in the orthorhombic space group Cg:-Ibm2 with a = 6.049,
b = 15.84, and c = 5.81 A and is isotypic with Ca,FeAIO,.llS A second
strontium indate, SrIn204, has space group Di;-Pizam with a = 9.809,
b = 11.449, and c = 3.265 A. The structure consists of a framework containing groups of two edge-linked octahedra with intercalated Sr2+ions.l16 The
formation of a new strontium oxothallate, Sr4TI,07, is claimed which is
prepared from 1: 4 Tl,Q,-SrO mixtures in a sealed vessel after several days
at 600 OC. Annealing for two months at 550 OC provides tetragonal single
crystals, space group C&-P4,rzm,with a = 5.006 and c = 18.73 A. Sr atoms
are surrounded by six 0 atoms arranged in trigonal prisms with Sr-0
distances ranging from 2.52 to 2.79 A.117 Strontium perthiocarbonate is
prepared by treating a suspension of Sr(OH),,8H20, previously saturated
with H,S, with an excess of CS, and S,and drying the resulting precipitate in
vacuum. SrCS, can form di-, tri-, and tetra-hydrates. Thermal decomposition
gives SrS, and CS2 but the process is complex. SrCS, is inert to dry oxygen
up to the decomposition temperature, 100 'C,when rapid oxidation occurs
to SrSO,. In moist air, SrCS, is transformed into thiosulphate.ll*
The complex silicophosphates Sr4M6(Si04)4(P04),0,(M = La, Nd, Y,or
Er) have been synthesized. These compounds have been shown by X-ray, i.r.
spectroscopic, and crystallo-opticalanalyses to belong to the apatite structure.
The properties of the synthesized compounds depend linearly on the arithmetic mean of the ionic potentials of the cationic and anionic cornponents.ll9
The Sr-Sb system contains at least five compounds, Sr,Sb, Sr5Sb3,Sr3Sb2,
SrSb, and SrSb,. These have been identified previously. More recently the
structure of the most metal-rich of these compounds, Sr2Sb,has been assigned
as tetragonal, space group I4/mmm with a = 5.002 and c = 17.405A and
d(ca1c) == 4.528 for Z = 4. The structure contains uncommonly short
Sr-Sr distances as shown in Figure 5. There are layers (A) containing only
coplanar Sr(1) atoms in a cubic arrangement. Between two successiveA layers
there are two more layers (B), each one containing Sr(2) and Sb atoms. The
atoms in the B layer are not exactly coplanar as the Sr(2) atoms are 0.61 A
above the plane. Each Sr(1) has twelve neighbours arranged as shown in
lls
116
11'
119
T. Nagai and M. Ihara, Y o g p Kyokai Shi,1972, 80,432.

R. Von Schenck and H. Mueller-Buschbaum,Z . anorg. Chem., 1973,395,280.
R. Von Schenck and H. Mueller-Buschbaum,2. anorg. Chem., 1973, 398, 24.
R. Von Schenck and H . Mueller-Buschbaum, 2.anorg. Chern., 1973, 396, 113.
D. Zins and M. Robineau, Compt. rend., 1973, 267, C , 951.
N. F. Fedorov, I. F. Andreev, and Sh. Yu. Azimov, Zhur. neorg. Khirn., 1972,17,2926.
94

A
8 =sr
O =Sb
B
Figure 5 Sequence of layers of atoms in the structure of Sr2Sb.
Figure 5. These are four Sr(2) (at 3.898&, four Sb (at 3.451 A), and four
Sr(1) atoms at the very short distance of 3.537A. The atomic distribution
around the Sr(2) atoms in the B layers consists of thirteen atoms, four Sb
(at 3.589 A) in its own B layer, one Sb (at 3.335 A) and four Sr(2) (at 4.464 A)
in the adjacent B layer, and four Sr(1) (at 3.898 A) in the adjacent A layer.
The average Sr-Sb distance of 3.499 A is appreciably smaller than the value
of 3.70 A obtained from the sum of the metallic radii (Pauling) and assuming
co-ordination numbers of 9, 12, and 13 for Sb, Sr(l), and Sr(2) respectively.
This, together with the small Sr(1)-Sr(1) distance, indicates a pronounced
deviation from metallic behaviour towards a partial ionic character for these
atoms.120
The crystal structure of strontium dithionate tetrahydrate, SrS20,,4H20,
belongs to the space group P62 with a = 6.32 and c = 19.29A and 2 = 3.
Each Sr atom is bound to eight 0 atoms at an average distance of 2.58 f
0.04& whereby only two of the three independent 0 atoms of the SO,
groups are co-ordinated. No hydrogen-bonding is perceptible. The S-S and
S-0 distances are 2.15 and 1.41 A respectively.121A study of the structural
chemistry of ternary tellurides of alkaline-earth or alkali metals with Group 111
elements reveals the new compounds M1M22Tep(M1= Sr or Ba, M2 = Al,
Ga, or In), Ba,A1,Tel,, NaInTe2, and KInTe2, which all have a tetragonal
structure with space group D~-:-I4/mcm
and lattice constants a = 8.21-8.52
and c = 6.72-7.39&
except Ba,Al,Te,, which has a = 34.24 and c =
6.70A. The compounds are prepared by solid-state reaction of the elements
120 M. Martinez-Ripoll, A. Hasse, and G. Brauer, Actu Cryst.,
lS1R. N. Hargreaves and E. Stanley, Z . Krist., 1972, 135, 399.
1973, B29, 1715.
95
for 12 h at 1050-1200 OC under a pressure of 10 Tom of argon.122 The
alkaline-earth halide hydrates SrC12,6H20,SrC12,2H20,SrCl,,H,O ; SrBr,,
6H20, SrBr2,H20; SrI,,GH,O, SrI,,H,O; BaC1,,2H,O, BaCI,,H,O; BaBr,,
2H20, BaBr,,H,O; BaI,,GH,O, BaI,,2H20, and BaI,,H,O have been studied
by d.t.a. and i.r. spectroscopy. The dehydration temperature decreases with
increasing size of cation and increases with increasing size of anion.123
From the temperature dependence of the i.r. spectrum of difluorenylstrontium in THF at 20 to -100 OC it is deduced that the ion triplet, F1-Sr2+
F1-, is solvated in two steps,
Fl-Sr2+Fl- = F1-
11 Sr2+F1-= Fl- 11 Sr2+11 F1-
in which the Sr cation is successively separated from the two fluorenyl carbanions. The first and second steps have enthalpies of -12.3 f 2 and
-2.8 f 1 kcal mol-l and entropies of -47 f 7 and -17 f 5 cal deg-l
m01-l.l~~Strontium dipicolinate tetrahydrate, SrC,H3N0,,4H,0 is monoclinic, space group C2/c, with a = 10.698, b = 12.827, and c = 8.394A,
/? = 98.75', d = 1.89, and Z = 4.125
Complexes of strontium salts with urea
(L), CO(NH,),, are reported. These are SrC12,4L, SrCI,,2L,H,0,126 and
Sr(ClO,),, 5L,Sr(Clod, ,2L, and Sr(CIO,), ,L.12'
5 Barium
Distillation and crystallization are effective processes for the removal from
barium of Na, K, Mg, Ca, Sr, Al, Si, Sb, Bi, Mn, Fe, and Cu.12*The temperature dependence of the electrical resistivity of barium (and Y) has been
measured at 5 140 kbar. Based on the negative curvature of the resistivitytemperature relation with increasing pressure, it is suggested that Ba attains
d-metal characteristics at high pressures.129A new structural variant of the
BaAl type is shown by the ternary intermetallic compounds BaMg,Pb,,
BaZn,Pb,, and CaBe2Ge2.These compounds are prepared from the elements
by melting under argon. The isotypic crystals belong to the space group
E. R. Franke and H. Schaefer, 2. Naturforsch. 1972, 27b, 1308.
H. D. Lutz, H. J. Klueppel, F. J. Marner, and H. J. Kesterke, 2. Naturforsch., 1973,
28b, 8.
la4T. E. Hogen-Esch and J. Smid, J . Amer. Chem. SOC.,1972,94,9240.
125 F. T. Jones and R. Wong, Microscope, 1972, 20, 327.
12* S. Isakova, K. Nogoev, and K. Sulaimankulov, Zzuest. Akad. Nauk Kirg. S.S.R., 1972.
66.
12' N. N. Runov and V. P. Zakharova, Uch. Zap., Yaroslau. Gos. Pedagog. Inst., 1972,
No. 103, p. 67.
128 V. G. Khudaiberdiev, V. N. Vigdorovich, and A. V. Vakhobov, Sbornik Nauchn.
Trudov Probl. Mikroelektron., Moskov. Inst. Elektron. Tekh., 1972, No. 8, p. 44,
(Ref. Zhur., Khim., 1972, Abs. No. 17L79).
lagA. R. Moodenbaugh and Z . Fisk,Phys. Letters (A), 1973,43, 479.
122
123

96
P4lnmm with a and c, respectively, 5.00 and 12.11, 4.69 and 11.33, and 4.02
and 9.92 A, with 2 = 2.130 The enthalpy of formation of BaAI, is 29.6 kcal
m01-1?31
The compound of approximate composition BaO,Al,O,,H,O has a structure based on a framework of empirical formula A102. The Ba atoms are
distributed over a number of sites in the cavities, which also contain the
remainder of the A1 atoms.132Barium indium oxide, Ba41n6013,is prepared by
heating the mixture 4BaC0,
31n20, in air at 1000 OC for 2 h. To homogenize, the sample is ground, pelletized, sintered in air at 1250 OC for a further
2 h; and subsequently quenched in air. The crystallographic parameters for
the orthorhombic compound are a = 11.899, b = 20.567, and c = 5.975 A,
d(expt) = 6.45, and d(ca1c) = 6.58 for 2 = 4.13,
The structure of barium tin disulphide, BaSnS,, is a distortion of the
sodium chloride type. The space group is P2Jc with a = 6.0848, b = 12.1396,
and c = 6.2356& and /I= 97.058'. The structure can be considered as a
composite of the Bas and SnS structures, both of which are based on the
NaCl motif. Barium is in six-fold co-ordination in a slightly distorted octahedron of sulphur atoms. Tin is also enclosed octahedrally but is positioned
close to a triangular face of S ions so that it is bonded to three S atoms only.
In this polar arrangement Sn can be considered to have a tetrahedral environment in which a lone pair of electrons occupies one vertex. The cations are
ordered so that Ba layers alternate with Sn layers in the overall NaC1-type
ar~hitecture.~,~
The thermal decomposition of barium bis(oxalato)stannate(n),
Ba[Sn(C,04),],0.5H,0
(6) and barium tetrakis(oxalato)stannate(Iv),
Ba[Sn(C204)4],6H20(7) has been followed by t.g.a., d.t.a., evolved-gas
analysis, X-ray diffraction, and Mossbauer spectroscopy. In both cases,
decomposition in air or oxygen proceeds through an intermediate mixture of
BaCO, and SnO,. In the absence of air, tin reduction and subsequent reoxidation occur. The final products of the decomposition of (6) and (7) are
BaSnO, and Ba,SnO, respectively. High-purity BaSnO,, suitable as a
Mossbauer source, can be prepared free of BaCO, by starting from (6).135
The hydrazine derivatives SrN,H2 and BaN,H, thermally decompose at
190C under decalin to give 100% amorphous phases of SrN,.,H,., and
BaN,.,H,.4 respectively. The phases are characterized by hydrolysis with HCl
and, in the case of BaN,.,H,.,, by reaction with a ~ e t 0 n e . The
l ~ ~ pernitride
Sr,N, is weakly diamagnetic whereas Ba,N4 and Ca3N4are paramagnetic at
77, 195, and 293 K. The i.r. spectra of the reaction products of Ba3N4with
CO at 5O-25O0C and high pressure show no exchange with nitrogen but
130
131
B. Eisenmann, N. May, W. Mueller, and H. Schaefer, 2. Naturforsch., 1972,27b, 1155.

V. N. Vigdorovich, A. V. Vakhobov, and Yu. V. Plotnikov, Zhur.fiz. Khim., 1972,46,
1426.
132
133
13*
135
136
A. H. M. Ahmed, L. S. D. Glasser, and M. G. King, Acta Cryst., 1973, B29, 1166.

F. Kanamaru and M. Koizumi, J. Amer. Ceram. SOC.,1973, 56, 399.
J. E. Iglesias and H. Steinfink, Acta Cryst., 1973, B29, 1480.
P. K. Gallagher and F. Schrey, ref. 63, p. 623.

K. H. Linke and R. Taubert, Z . anorg. Chern., 1972,393,253.
97
partial addition of CO. At 250 C and 450 atm of CO, Ba,N4 forms Ba(CN),
in high ~ie1d.l~
The enthalpies of solution of barium monoxide, BaO, and of barium metal
in 1M-HCl are -65.29 f 0.23 and -127.95 f 0.41 kcal mol-l respectively.
From these results, the enthalpy of formation of BaO(s) is calculated to be
AH;,298 = 130.98 f 0.47 kcal m01-1.138 The dissociation energy, as determined by electron bombardment, is 92 =t 5 kcal mol-l. The ionization potential of Ba is 5.21 eV. These results agree with published data.139The rate of
reduction of barium sulphite, BaSO,, with hydrogen has been studied from
640 to 720C. The experimental data fit a mechanism of two consecutive
reactions, the disproportionation of BaSO, and the subsequent reduction of
The rate constant for disproportionation
BaS04 with H, to produce
is 50-100 times greater than that for BaSO, reduction. The effective activation energies are 45.7 kcal mol-l for the disproportionation and 30.3 kcal
mol-l for the reduction process. The presence of H, in the gas phase has a
significant catalytic effect on the disproportionation of BaSO,; the rate
increases nearly linearly with the partial pressure of H,. The presence of H 2 0
vapour reduces the rate of reduction of Ba,S04 by hydrogen.141The lattice
parameters of orthorhombic barium thiotellurite, BaTeS,,2H20, with space
group Pbcm are a = 7.11, b = 7.63, and c = 13.60A, d(expt) = 3.5, and
d(ca1c) = 3.52 for 2 = 4. The Ba2f ions are co-ordinated by six S and four
H,O molecules. The structure contains TeS, groups which form layers
parallel to a, b which are separated by Ba2f ions and water molecules.142
The enthalpies of formation, AHf/kcalmol-l, of the mono- and dihydrates and deuteriates of barium chloride have been determined as
BaCl,,H,O(s), -277.18 ;BaC12,2H,0(s), -348.98 ;BaCl,,D,O(s), -279.09 ;
and BaC1,,2D2O(s), -353.27. The standard enthalpies of dehydration and of
D,O exchange between these compounds are given below
BaCl,,nX,O(s)
--+
BaCl,,(rz
- l)X,O(s)
+ X,0(1)
1
2
D
H
D
2
BaCl,,nX,O(s)
BsCI,,nH,O(s)
--f
BaCl,,(n
+ nD,O(g)
- l)X,O(s)
--+
+ X,O<g)
BaCl,,nD,O(s)
+ nH,O(g)
1
1
2
2
1
2
D
H
D
AHo
kcal mol-1
3.660
3.480
3.490
3.410
14.180
14.330
14.010
14.260
-0.150
-0.400
13
13*
K. H. Linke, R. Taubert, and Th. Kruck, Z . anorg. Chem., 1973, 396, 1.

G. C. Fitzgibbon, E. J. Huber, and C. E. Holley, J . Chem. Thermodynamics, 1973, 5 ,
139
140
141
14,
I. G. Panchenkov, A. V. Gusarov, and L. N. Gorokhov, Zhur.fiz. Khim., 1973,47,101.

K. Mocek and E. Erdos, Coll. Czech. Chern. Comm., 1972, 38, 7.
K. Mocek and E. Erdos, Coll. Czech. Chenz. Comm., 1972, 38, 16.
H. Gerl and H. Schaefer, 2. Naturforsch., 1972, 27b, 1421.
577.
98
There is a 1-2% enhancement of the enthalpies of hydration of barium

chloride by the substitution of D,O for H,O but it is impossible to determine
whether this is a primary isotope effect resulting from changes in the strengths
of the interactions of H atoms with neighbouring atoms or a secondary effect
involving the interaction of the 0 atoms.143
The alkaline-earth metal salts form complex cryptate-type compounds
analogous to those formed by the alkali-metal salts (see Chapter 1 :complexes
of alkali metals). The bivalent metal ions, however, can take both water
molecules and anions into the cryptate cage. Two compounds containing Ba
and one containing Ca have been reported. The structures of these compounds are detailed in Table 2. In (8) and (9), the cryptate molecule is of the
Table 2 Structural parameters for cryptate complexes of calcium and barium

Structure
Complex
C~SH~~N~O~,C~B~,,~H,O
(8) orthorhombic
C1BH36N20B,Ba(SCN)2,Hz0 (9) orthorhombic
C20H40N20,,Ba(SCN)2,2H20
(10) monoclinic
Structure
Complex
(8) orthorhombic
ClsH36N20s,Ba(SCN)2,H20(9) orthorhombic
C20H40N20,,Ba(SCN),,2H,0
(10) monoclinic
Space
group
a/.bi
b[.bi
P212121 19.200 14.518

37.728 19.525
Pbca
P2Jc
11.580 16.030
Space
group
CIA
P2,2,2,
Pbca
P2Jc
9.511
15.303
19.563
4
16
4
type (1 1). In (10) the cryptate molecule contains an extra (-CH,-0-CH-)

group in one of the bridges (12). In the calcium compound (8), the Ca2+ion is
bonded to the six 0 and N atoms of the macrobicyclic ligand and to one H,O
molecule, which together constitute a tricapped trigonal prism. Thus the
complex cation is [Cl,H,,N,O,,Ca,H,O]+.
The mean Ca-0 distance is
2.52 A whereas that for Ca-OM, is 2.41 A. The Ca-N separations are
(1 1)
(12)
2.720 and 2.722 A. The Ca-Br distances are greater than 5.0 A, indicating
that there is no interaction between the Ca2f and Br- ions. The anions,
however, are in contact (3.25, 3.27A) with the water molecule in the complexed ~ a t i 0 n . l ~ ~
143
14*
L. E. Smith and G. L. Bertrand, Thermochim. Acta, 1973, 5 , 451.

B. Metz, D. Moras, and R. Weiss, Acta Cryst., 1973, B29, 1377.
99
In (9), the alkaline-earth cation Ba2+ is again enclosed by the cryptate
molecule; it is bonded to the eight heteroatoms and one H20molecule, but in
this complex it is also bonded to one SCN- anion through the N atom. Again
the cryptate molecule does not completely displace the cation hydrate sphere,
and does not avoid cation-anion interactions. The Ba2+ ion resides in a
distorted trigonal prism capped at each triangular face by an N atom of the
cryptate molecule. Two of the lateral faces are occupied by an H,O and an
SCN group respectively. The ten-co-ordinate Ba2+ion has six 0 atoms at a
mean 2.80& an OH2 molecule at 2.86& and two N atoms at 2.944 and
3.002A distant. The latter are longer than the average Ba-NCS distance
of 2.895 A. There are two crystallographicaIly independent complex cations,
[C,H,,N,0,,Ba(SCN),H20]f, which are linked together by an hydrogenbonded system involving the non-complexed anions SCN- (13).145
Ba
B?
'. 2.87
';,2.88
.S
*.
2.84
Ba
*.2.81
(13)
Ba
(14)
In (lo), the Ba2+ cation is again held within the molecular cavity of the
cryptate molecule and is eleven-co-ordinated by nine heteroatoms of the
ligand and two H20 molecules. In this compound, however, no SCNanion is contained within the ligand and the Ba2+ion is not situated precisely
in the centre. The average Ba-0 distance is 2.91 A, and Ba-N distances are
3.084 and 3.179 A. The uncomplexed SCN- ion is at least 5.15 A from the
Ba2+ion. The complex cations, [C20H40N207,Ba,
(H,O),]+, are linked together
by a hydrogen bonded system which involves the uncomplexed anions (14).
This arrangement differs slightly, however, from that in (9).146
6 Analysis
The methods available for the quantitative determination of the light nonferrous metals Be, Mg, Al, and Ti have been reviewed. The acid-base
properties of non-aqueous solutions of beryllium bromides with other
146
146
B. Metz, D. Moras, and R. Weiss, Acza Crysf., 1973,B29, 1382.

B. Metz, D. Moras, and R. Weiss, Acza Crysf.,1973, B29, 1388.
100
bromides have been investigated in 25: 1 Me,CO-BuOH mixtures. In this

medium, bromides behave as acids of different strength and BeBr, is titrated
potentiometrically with 0.1N-KOH in BuOH giving two titration breaks.14'
The alkali-metal bromides do not show acid-base properties and do not
interfere. Be, Al, Sc, Y , Sn'I, and the rare earths (except La) behave as acids
of the same strength and thus cannot be determined by differential titration.
The start of the potential jump for Be differs considerably from that for many
other metals and thus there is a possibility of differential titration of their
mixtures. A method is developed for the automatic titration for Be.148The
absorption and fluorescence spectra of the Be complex with methyl derivatives
of 1-hydroxyxanthoneare generally similar though the 6-methyl-1-hydroxyxanthone complex shows the highest fluorescence intensity. A method of
determining Be with this material is developed from the spectral data.149
Beryllium can be determined gravimetrically as the bis (salicyla1dehyde)ethylenediamine Schiff base complex Be(C,,H14N,0,),2H,0. For least
interference, the presence of tartrate and ammonia is necessary.15* New
chelating agents 0-(2-hydroxy-5-dodecylphenylazo)benzoic acid and the
corresponding phenylarsonic acid have been prepared. These compounds in
petrol or chloroform are used as liquid ion-exchangers for the separation of
Be and Al.151Beryllium complexes with carboxylic acids, e.g. palmitic acid,
and the basic dye Rhodamine B (L). The Be:acid:L ratio in the complexes is
1 :3 :1. The complex can be extracted at pH 4--9, the best extraction occurring
with toluene at pH 5.5-6.0. Spectroscopically,the maximum absorbance of
the complex containing palmitic acid is at 540nm; that with phenol is at
550 nm.152The optimum conditions for the extraction of Be from its aqueous
solutions containing H2S04and NH4NCS by isobutyl ketone solutions of
tri-n-octylamine (A) are NH,CNS 2M, A 0.3M, and pH 2.6-2.9 at 20 "C.
Beryllium is extracted as [AH+]pe(NCS):],2AHNCS into the organic phase.
The separation of Be from Mg, Al, and Zn can be quantitative.153Beryllium
and the other elements of Group I1 can be extracted by tri-n-butyl phosphate.
At 22 "C, the extraction of the metals (M) from aqueous solutions with initial
concentrations 2M-M(N03), by Bu,P04 (50 ~ 0 1 % in
) kerosine decreases in
the order Ca > Be > Sr > Mg. For aqueous solutions more concentrated
than 2M-M(N03)2,the extraction decreases in the order Ca > Be > Mg >
Sr. In all cases the extraction of the metals is small, with partition coefficients
D(M)= [M]OTg/[M]ag
< 0.1.154 The effect of temperature (10,20, and 30 "C)
14'
148
149
150
151
152
153
154
R. Danchik, Analyt. Chem., 1973,45, 113R.

A. P. Kreshkov, S. M. Milaev, and M. M. Baldanov, Zhur. analit. Khim.3 1972, 27,
2349.
A. Murata and M. Nakamura, Bunscki Kagaku, 1972,21, 1365.
B. R. Singh and S. Kumar, Indian J . Chem., 1972, 10, 663,
E. Blasius and H. J. Finkenauer, Talanta, 1973, 20, 639.
N. S. Poluektov, S . Meshkova, S. V. Bel'tyukova, and E. I. Tselik, Zhrrr. analit. Khim.,
1972, 27, 1721.
A. V. Novoselova, N. S. Tamm, T. I. Pochkaeva, and N. V. Likhanskaya, Vestnik
Moskov Univ., Khim., 1973, 14, 55.
G . Brunisholz, W. Hirsbrunner, and J. Aerny, Helv. Chim.Acta, 1972, 55, 2956.
101
on the distribution and dissociation constants for acetylacetoneand beryllium
acetylacetonatehas been examined in the H,0-CC14 solvent mixture. For the
beryllium complex, the equilibrium distribution is reached more quickly the
higher the temperature for equal pH values. Increasing the pH also hastens
the extraction. The logarithms of the extraction constants for beryllium
acetylacetonate are -2.95, -3.17, and -3.35 at 10, 20, and 3OoC respectively.155
The amount of hydrogen in magnesium can be determined by a method
which is reminiscent of that commonly used for sodium. The metal is sealed
in a capsule of pure iron with thin walls (0.3 mm). At 500-550 "C under
vacuum hydrogen is evolved and diffuses through the iron walls of the
capsule in a matter of minutes. Any other gases are filtered out by a palladium
thimble and the hydrogen is determined by pressure mea~urernent?~~
calcium in water and ethanol is based on
A determination of 1 x
the formation of a green fluorescent calcium complex with 8-hydroxyquinaldine carboxaldehyde 8-quinolylhydrazone in 0.1N-KOH. Strontium
( < 2 rug), barium( Q 20pg), and magnesium ( Q 20pg) do not interfere but the
fluorescence of the complex is decreased by other e1eme11ts.l~~
Calcium (and
zinc) form complexes with methylthymol blue in a 1 :1 ratio at pH 11 (and 6)
with maximum absorbance at 610 (and 584)nm. Beer's law is obeyed for
< 50 pg Ca per 50 ml. The anions C1-, NOT, and SO:- (4000:1) do not
interfere.158 Calcium (and boron) can be extracted from (>30 %) aqueous
solutions of MgCl, with 4-t-butylcatechol dissolved in kerosine containing a
higher alcohol. Boron is extracted as a catechol-borate anion for which Ca
serves as the counter ion. The extracted Ca is solvated by the excess 4-tbutylcatechol and extraction is pH-dependent. Removal of these species
from the organic phase is readily accomplished with dilute mineral acid. In
the absence of ByCa can be extracted alone as solvated CaCl, and removed by
treatment with water alone. Selectivities of the solvent for Ca over Mg close
to 1000 are 0 b ~ e r v e d .Azol ~ ~ or azoxy-benzene in CCI, with 20 vol % tributyl
phthalate can be used for the separation of calcium from scandium. Complex
formation occurs with bivalent metals but not tervalent metals; hence Sc
alone or in the presence of Ca does not react with the azo-compound. Sc in
concentrations up to 5 ,ug ml-l does not disturb the extraction.160Extraction
of CaySr, and Ba (<1 g equiv. 1-l) from their aqueous solutions containing
NH,OH (<8M), NaOH (<5M), NaNO, (0.1-l.OM), and NH,NO,
(<2M) by Bu,PO4-CC1, solutions of salicylaldoxime (L) has been studied
155
156
15'
158
159
160
A. F. Kuznetsov, A. I. Sevast'yanov, and N. P. Rudenko, Khim. Protsessov Ekstr.,

Muter. Konf. Khim. Ekstr., 3rd, 1969 (publ. 1972), 254.
V. A. Danilkin, Zavodskaya Lab. 1972, 38, 719.
L. F. Fedorova and E. A. Bozhevol'nov, Metody Analit. Khim. Reaktiv. Prep., 1971,
No. 18, p. 7 (Ref. Zhur., Khim., 1971, Abs. No. 24G322).
G . A. Butenko, A. S. Grzhegorzhevskii, and I. G. Sturre, Voprosy Khim. khim.
Tekhnol., 1972, No. 27, 131.
R. R. Grinstead, Ind. and Eng. Chem. (Product Res. and Development), 1972, 11, 454.
F. P. Gorbenko, E. V. Lapitskaya, and N. I. Loshkareva, Radiokhimiya, 1973,15,261.
102
at 2O--8O0C. The metals are extracted into the organic phase as CaLz,
SrL2,Bu,P04, and BaL,,BuP,O,. The distribution coefficients of Ca, Sr, and
Ba do not depend on the initial concentration of the metals if the concentration is less than 0.05 g equiv. 1-l.161 The extraction has also been investigated
of Ca, Sr, and Ba (<0.1 g equiv 1-l) from aqueous solutions containing
NaOH (<3N), NH40H (<5N), K,Cr04 (<O.lN), NH4N0, (<3N), or
NaNO,, at pH 1-12 by CHCl, solutions of Ba,PO, (0.14.OM) and 5,7dichloro-8-quinolinol (O.O2M), 5,5-dibromo-8-quinolinol (0.02M), 5,7-dibromo-8-quinolinol (0.02M), or 5,7-di-iodo-8-quinolinol (0.02M). The
distribution coefficient of the oxines between the organic and aqueous phases
is 40-1 10 at pH 1-12. The distribution coefficient of the metals decreases in
the sequence Ca > Sr > Ba at all pHs studied.162 Spectrophotometric
measurements on the Ba and Sr complexes of Sulphonazo I11 reveal that pH
has no effect on the complexes over the range 2.6-7.7. The addition of
trans-l,2-diaminocyclohexane-NNNN-tetra-acetic
acid eliminates the interference of most cations except Cu, which forms a light-blue complex. Simultaneous determination of Sr and Ba is possible using simultaneous equations
derived from Beers Law. The working range for the method is 1.0-3.0 x
low5M for Ba and 2.0-8.0 x 10-6M for Sr. An aqueous solution of Sulphonazo 111 shows <1% decomposition over seven days.163 A lead-selective
electrode has been used as an indicator electrode for SO:-. The anion is
titrated with Ba(C104),, and Sr and Ba are titrated with Na2S04at pH 5-7
in dioxan-H,O mixtures. The detection limits are 5 x 10-4mmol for Sr,
Ba, and
Yu. Z. Prokopchuk, N. E. Brezhneva, G. V. Korpusov, and N. P. Prokhorova,
Radiokhimiyn, 1973,15,42.
laaYu. Z. Prokopchuk, G. V. Korpusov, and N. E. Brezhneva, Radiokhimiya, 1973,15,
35.
163 P. J. Kemp and M. B. Williams, Analyt. Chem., 1973,45, 124.
16* C. Harzdorf, 2.analyt. Chern., 1972,262, 167.

BY G. DAVIDSON
1 Boron
General.-A short review1 has appeared on the preparation and physical

characteristics of crystalline boron.
The reduction of BCI, by H, in an argon induction plasma produces boron
with an impurity level of <0.4% in yields of 70-75%.2
Carefully controlled reduction of BBr, with H2 on Ta wires in the range
1100-1400 "C gives two different crystalline polymorphs of elementary
boron, depending upon the temperature. At ca. 1150-1200 "C II-tetragonal
boron, Bls2 (space group P422; a = 10.12, c = 14.14A), is produced,
whereas at approx. 1400 OC p-rhombohedra1 boron, B105 (space group
R3m; a = 10.94, c = 23.81 A), result^.^
High-temperature enthalpies of boron have been measured by drop
~alorimetry.~
The enthalpy of fusion was found to be 12.0 f 0.4 kcal
(g atom)-l, with the entropy of fusion 5.1 cal (g atom)-l K-l (at a m.p. of
2350 K). The latter is more than twice as large as values estimated from
previous experiments.
Measurements have been made of the kinetics of reaction of HBr with
elemental boron in the temperature range 600-900 "C, and the [HBr] range
5 x lo-, to 24 x
atm.5
McFarlane has demonstrated that the 1B-llB isotope effect upon the
boron nuclear shielding is extremely small, and that it may be regarded as
being effectively negligible.6
Ab initio LCAO-MO-SCF wavefunctions (of near-Hartree-Fock accuracy) have been obtained for the systems BCN, BNC, BCC, CBC, BBC,
and BCB.'
'
F. Tavadze and G. Tsagaireshvili, Soviet Sci. Rev., 1972, 3 , 357.

J. Cueilleron and B. Cruiziat, Bull. SOC.chim.France, 1973, 1207.
K. Ploog, J. Less-Common Metals, 1973, 31, IS.
N. D. Stout, R. W. Mar, and W. 0. J. Boo, High Temperature Sci., 1973, 5,241.
B. A. Saveliev, V. A. Krenev, and V. I. Evdokimov, Russ. J. Inorg. Chem., 1973, 18,
167.
W. McFarlane, J. Magn. Resonance, 1973, 10, 98.
C.Thomson, J. Chem. Phys., 1973,58,216.
103
104
ESCA measurements have been reporteds for 23 boron compounds

[BX, (X = F, GI, Br, I, Et, OMe, or OEt), ClBEt2, H,BNEtB,H2BNEt,,
(Me2N)zBB(NMe2)2 (1 1, R2Hf3, Prn4B2H2 p-B2H5NMe2 B5H9 1 5-C2B3H5
9
1 ,5-C2B,Et,, 1 ,6-C2BpH6,2,3-C2B,H,, 2,4-C2B,H,, 1 ,2-C2B10H12,and 1,7C2Bl,Hl,], and boron 1s binding energies measured in the vapour state.
These were related to the chemical reactivity of the compounds.
A new photometric method for the determination of boron using curcumin
has been devel~ped.~
Direct spectrophotometric determination of boron impurities in UF, is
possible if ZnO is added to the sample to delay the volatilization of the
uranium.1
Boron Hydrides.-Ground-state wavefunctions of BH have been calculated

using the GI and SOGI methods.ll Allowing rr-character in the orbitals
produced a significant improvement in the description of the system.
The use of average natural orbitals in configuration interaction calculations on the BH molecule has been discussed.12
MO calculations carried out on the BH, system have been used to calculate
harmonic force constants and vibrational frequencies for BH3.13
Some qualitative MO calculations on B2H, and C2H6 indicate that dimerization of both BH, and CH, should have zero or negligible activation energies.l*
SCF calculations, using a basis of all s-type Gaussians, carried out to
investigate the dimerization:
indicate a value of 11.5 kcal mol-l for the dimerization energy, whereas the
experimental value is ca. 50 kcal mol-l. This supports the assumption that
electron correlation plays a dominant role in the process.15
Upper limits for llB--llB nuclear-spin coupling constants have been obtained for a three-centre, two-electron B-H-B
bond in 11B2H6 ( G l . 1 Hz)
D. A. Allison, G . Johansson, C. J. Allan, U. Gelius, H. Siegbahn, J. Allison, and K.

Siegbahn, J. Electron Spectroscopy, 1973, 1, 269.
M. Vrchlabskf, COILCzech. Chem. Comm., 1972, 37, 3590.
l o F. A. Alduan, C. Capdevila, and M. Roca, Z . anulyt. Chem., 1973, 263, 128.
l1 R. J. Blint and W. A. Goddard tert., J. Chem. Phys,, 1972, 57, 5296.
la S. A. Koulden and I. G. Csizmadia, Theor. Chim. Actu, 1973, 30,209.
l3 M. Gelus and W. Kutzelnigg, Theor. Chirn. Acta, 1973, 28, 103.
l4 B. M. Gimarc, J. Arner. Chem. SOC.,1973, 95, 1417.
l5 C. Edmiston and P. Lundner, Internat. J . Quantum Chem., 1972, 7 , 309.

105
and 11B4H10 (< 0.3 Hz), under conditions of double and triple resonance,
respectively. These values are much less than that found in B5H9, and no
firm explanation of the difference was @veal6
H
/ \
Assignments have been proposed17 for the B
B ring-puckering
\ /
H
vibration in B2H6 (369 cm-l) and B2D6 (261 cm-l).

Low-temperature chemical ionization spectra of B2H6, B4H10, and B5H,
in methane have been obtained. Protonation of B2H, (-+B2H$) is observed
between 79 and 86 K, and the proton affinity of B2H6 is 147 f 4 kcal mol-l.
In B2H,-CH, and B,H6-H2, B,H& (from B2H6 B,H$) was formed
(between 80 and 140 K, 80 and 115 K, respectively). From the observed
heat of formation of this species the proton affinity of B4H10 was calculated to be 144 f5 kcal rnol-l.l*
Diborane, B5H9, l-BrB5Hs, and 2-BrB5H8 all catalyse the liquid-phase
condensation of N(SiH,),
MeN(SiH3)2,to give silane and silazane oligomers and/or p01ymers.l~
The wavefunctions for B4H4have been computed in the SCF-LCAO-MO
approximation.20Four central, three-centre B-B-B
bonds are predicted,
but these are, surprisingly, non-symmetric and non-equivalent. However,
B4H4should (by this calculation) be stable by 316.9 kcal mol-l with respect
to dissociation into B-H units. No very satisfactory reason for the experimental elusiveness of this species could be proposed.
lH, 2H, and llB n.m.r. spectral studies on tetraborane(lO), using isotopic labelling, have elucidated the mechanism of the intramolecular
hydrogen-exchange reaction for this moleculem21Two types of exchange
occur, the faster involving the bridging and four of the terminal hydrogens,
the slower the bridging and the remaining two terminal hydrogens (those
attached to the boron atoms 2 and 4). Possible mechanisms for both of these
were discussed.
Epstein has considered the possibilities for electrophilic and nucleophilic
substitutions in B4H10, B5H,, B5Hll, BsHlo, and B1oH14 using a topological
approach.22Thus, a topological study was made of the possible transition
states for a reaction; if no transition state has a topologically allowed
valence structure, then that reaction is said to be topologically forbidden.
This technique is not able to produce any information about, for example,
magnitudes of activation energies, but it is very much simpler than even
very approximate MO calculations.
l6
l7
lB
2o
a1
22
J. D. Odom, P. D. Ellis, D. W. Lowman, and M. H. Gross, Inorg. Chem., 1973,12,95.

W. C. Pringle jun. and A. L. Meinzer, J. Chem. Phys., 1972, 57, 2920.
R. C. Peirce and R. F. Porter, J . Amer. Chem. SOC.,1973, 95, 3849.
W. M. Scantlin and A. D. Norman, Inorg. Chem., 1972,11, 3082.
J. R. Hall jun., I. R. Epstein, and W. N. Lipscomb, Inorg. Chem., 1973, 12, 915.
R. Schaeffer and L. G. Sneddon, Inorg. Chem., 1972,11, 3098.
I. R. Epstein, Inorg. Chem., 1973, 12, 709.
106
Application of the exponential line-narrowing technique to partially

relaxed FT llB n.m.r. spectra of B4Hl0, B5Hs, B5Dg, B5H11, B6H12,BI0Hl4,
and n-BsH15has enabled much higher resolution to be achieved; much more
fine structure was visible than in earlier experiment^.^^
Thermal decoupling has been observed to occur between quadrupolar
nuclei (llBs) in B5H9,in a study of the lH-decoupled llB (32.1 MHz) n.m.r.
spectrwm .24
The photoelectron spectrum of B5Hg(obtained using a He I source) may
be assigned very satisfactorily using the results of a previously published
ab initio SCF-MO calculation (E. Switkes, I. R. Epstein, J. A. Tossell,
R. M. Stevens, and W. N. Lipscomb, J. Amer. Chem. SOC.,1970, 92, 3837).
Less sophisticated (INDO, CNDO) calculations gave a very poor fit with the
observed orbital energies.25
A correlation has been found26between llB chemical shifts and substituent
effects in substituted boranes, especially for substituted pentaboranes.
Coupling constants ( J I I ~ - Ihave
I ~ ) been measured for 1-XB,H8 (X = H,
C1, Br, I, Me, Et, CHMe,, or SiMe,): in each case the constant lay within
the range 13.8-25.1 Hz. Unsuccessful attempts were made to synthesize
compounds in this series with X = CN, C-CH, Ph, CMG, and CHBrMe.27
1-(Chlorosilyl)pentaborane(9)is prepared quantitatively by the reaction :
2BC1,
+ 6(1-SiH3B,H,)
-+
B2H6
+ 6[1-(ClSiHa)B6H8]
The new compound was characterized by mass-spectral, n.m.r. (lH and llB),
and i.r. data. Temperature dependence of the SiH, resonance in the lH n.m.r.
spectrum could be explained in terms of electric quadrupolar relaxation
effects.28
The following improved synthesis of B6HlOhas been reported:29
+ KH
K+ 1-BrB,H7 +
l-BrB,H8
K+ B6HloBr-
-78
O C
K+ l-BrB,H;
+ H,
-78 O C
dK+ BsHloBr-35 OC
+ KBr.
The yield is 75 % based upon the consumption of 1-BrB5H8,and purification

is simple.
Low-temperature l H and llB n.m.r. spectra of B6Hlo and 2-MeB5H, are
consistent with the following facts: (i) the bridge proton exchange is slow
on the n.m.r. time-scale; (ii) the spectra for B6H10 are consistent with the
23
24
25
26
27
28
29
A. 0.Clouse, D. C. Moody, R. R. Rietz, T. Roseberry, and R. Schaeffer, J . Amer.

Chem. Soc., 1973,95, 2496.
D. W. Lowman, P. D. Ellis, and J. D. Odom, J. Magn. Resonance, 1972, 8,289.
R. W. Jones and W. S. Koski, J. Chem. Phys., 1973, 59, 1228.
A. R. Siedle and G. M. Bodner, Inorg. Chem., 1972, 11, 3108.
D. W. Lowman, P. D. Ellis, and J. D. Qdom, Inorg. Chem., 1973,12, 681.
T. C. Geisler and A. D. Norman, Inorg. Chem., 1972, 11, 2549.
H. D. Johnson jun., V. T. Brice, and S. G. Shore, Inorg. Chem., 1973, 12, 689.

107
known solid-phase structure; and (iii) the static structure of 2-MeB&, lacks
a mirror plane of symmetry.30
Fe,(CO), reacts with BeH10 to give the novel complex [,u-Fe(CO),(B6Hl0)].
1.r. and llBFT n.m.r. data indicate that the structure of this involves coordination of the (OC)dFe to the unique basal B-B bond of B,H,,.31
Another complex of this type has been reported by the same group of
workers.32 [(B6H1U)2PtC12]
is a trans-, square-planar complex, with the Pt
bridge-bonded to the unique (4,5-position) basal boron atoms in each of the
B6H1, ligands. The bridged B-B bond is almost perpendicular to the
C1-PtCl axis. The complex crystallizes in the space group P2,/n, with a =
8.095(2), b = 11.144.(2),and c = 7.796(2) A, and = 93.9(1)'. Significant
bond lengths are: Pt-C12.313(3); Pt-B 2.27(2); B-B (all) 1.82 f 0.05 A.32
A computer program for the determination of elemental formulae of ions
found in low-resolution mass spectra has been used33to evaluate data alleged
to be due to theheptaboranesB7Hll, B,H12, and B7H13. Only the first appeared
to be genuine, the data believed to be derived from the other two apparently
being due to other, as yet unidentified, species.
A new heteroborane, 1-thia-cZoso-decaborane(9), B,H,S, has been prepared
It was characterized by i.r.,
by the pyrolysis of B9H,,S at 375 "C in
mass, and llB n.m.r. spectral data; the proposed structure is (2). The compound is reasonably stable in air, and it is unattacked by water or aqueous
acids and bases.
(2)
30
31
32
33
34
V. T. Brice, H. D. Johnson jun., and S. G. Shore, J.C.S. Chem. Comm., 1972, 1128.
A. Davison, D. D. Traficante, and S. S. Wreford, J.C.S. Chem. Comm., 1972, 1155.
J. P. Brennan, R. Schaeffer, A. Davison, and S. S. Wreford, J.C.S. Chem. Comm.,1973,
354.
E. McLaughlin and R. W. Rozett, Inorg. Chem., 1972,11, 2567.
W. R. Pretzer and R. W. Rudolph, J. Amer. Chem. Soc., 1973,95, 931.

108
An unstable nonaborane B9H13 has been detected mass-spectrometrically
in a study of the pyrolysis of BgH& compounds in reactors directly coupled
to a mass spe~trometer.~~
Some reactions of n-nonaborane(l5) have been
together with
llB n.m.r. spectra of the products. Acetonitrile gives a symmetrical cleavage
reaction :
n-BgH15 2MeCN 3 B,H12NCMe (BNCMe),
while NH, causes deprotonation and rearrangement, giving the known ion
B9HG (derived from i-BgH15). No halogen derivatives of n-BgH15 could be
prepared.
Hydrogenation of (R2S)2B,oH12in the presence of BCI, or MeI, or with
heating, gives B10H14 (yields 30-68%). The action of D2 leads to the
formation of Bl0H,,D2, with the D atoms in the 5-, 6-, and p-po~itions.~~
Eight symmetrically deuteriated derivatives of B10H14 (p-BlOH,,D4,
1,2,3,4-B1oHloD, ; ~-1,2,3,4-B,oH6DS; 5,7,8, 10-BlOH10D4; 1,2,3,4,5,7,8,10BloH6Ds; p1,2,3,4,5,7,8,1 O-B,oH,D12 ; p-6,9-B1,H8D6, and 6,9-Bl,H12Dz,
Figure 1 The molecular structure of, and nuruiberiig systemf o r , 5,6-p-diphetiyl

p hosphino-decaborane(14). Boron atoms are represented by open
circles, carbon atoms by shaded circles, hydrogen atoms by small
shaded circles, and the phosphorus atom by a large open circle
(Reproduced by permission from Inorg. Chem., 1973, 12,288)
35
36
37
L. Cardini and T. P. Fehlner, Znorg. Chem., 1973, 12, 798.

R. Schaeffer and L. G. Sneddon, Znorg. Chem., 1972,11, 3102.
S. Hefmhnek, J. PleSek, B. Stibr, Z. JanouSek, and T. Hanslik, Coll. Czech. Chem.
Comm., 1972,37,4001.
Elements of Group H I
109
were prepared, and their i.r. spectra obtained (4004000cm-l). An approximate vibrational assignment was proposed, using these data.38
IlB-llB double-resonance experiments on 6-methyldecaborane(14) have
been used to obtain less ambiguous assignments of the observed llB chemical
shifts. Such a technique, it is believed, will give generally useful results of this
nature.39
The compound 5,6-,uu-diphenylphosphino-decaborane(14),B,,H,,(PPh,),
crystallizes in the orthorhombic space group P2,2,2,, with a = 7.39(1),
b = 12.59(1), c = 20.02(2) A, and 2 = 4. The P atom of the diphenylphosphino-group occupies a bridging position between B(5) and B(6) of a
distorted B,, icosahedral fragment. This confirms for the first time the substitution of a non-metallic atom in a bridge hydrogen position in the decaborane(l4) molecule - the molecular structure is shown in Figure l
The accidental degeneracy in the 70.6 MHz llB n.m.r. spectrum of 2(2'-pentaboran-2-yl)pentaborane(9) has been resolved by obtaining a series of
partially relaxed FT spectra. The spectrum then reveals one singlet and
3 doublets, in accord with the predicted structure (3).4l
Tridecaborane(l9), B13H19, occurs as a minor product of the pyrolysis of

B&t,O. Its crystal structure has been determined and this shows that it may
be described as an n-B,M,, cage which shares the B(3) and B(9) positions with
two basal borons of B,Hlo-see Figure 2.42
A new crystalline borane has been produced by the reaction of i-B9H15
with B6H10 at 0 "C:
Pentadecaborane(23) is a white crystalline material, air-sensitive but with

moderate thermal stability. A 70.6 MHz llB n.m.r. spectrum was in agreement
with the above formula, and the new species is regarded as an acid-base
38
39
40
41
42
F. Hanousek, B. Stibr, S. HeTmanek, and J. PleSek, Coll. Czech. Chem. Comm.,

1973,38, 1312.
R. F. Sprecher and J. C. Carter, J . Amer. Chem. Soc., 1973, 95, 2369.
L. B. Friedman and S. L. Perry, Inorg. Chem., 1973, 12, 288.
R. R. Rietz and R. Schaeffer, J. Amer. Chem. SOC.,1973, 95,4580.
J. C. Huffman, D. C. Moody, J. W. Rathke, and R. Schaeffer,J.C.S. Chern. Comm.,
1973, 308.
110

n
Figure 2 Molecular structure of tridecaborane(l9)

(Reproduced from J.C.S. Chem. Comm., 1973, 308)
adduct, in which the two B frameworks may be held together by a threecentre bond.43
Borane Anions and their Derivatives.-A number of rules, analogous to the
18-electronrule of organo-transition-metal chemistry, have been proposed for
metalloboranes. Thus, (i) a cluso-, n-vertex polyhedral heteroborane with one
transition-metal vertex requires 2n 14 electrons, (ii) nido-polyhedra of this
type require 2n + 16 electrons, and (iii) closo-polyhedra with two transitionmetal vertices require 2n + 26 electrons. Further rules can also be derived for
commo-compounds in which two closo-polyhedra are fused at the metal
atom.44
Hydrogen-deuterium exchange accompanying protolysis and deuterolysis
of BH; and AlHy ions is consistent with the intermediate formation of
BH, and
BH, is isoelectronic and isosteric with the methonium ion
CH;, and theoretical calculations ( C N D 0 / 2 method) favour a Cs structure
(4). According to these data, electrophilic attack on BH; (or AIH;) is at the
43
44
J. W. Rathke and R. Schaeffer, J. Amer. Chem. SOC.,1973,95, 3402.

C. J. Jones, W. J. Evans, and M. F. Hawthorne, J.C.S. Chem. Comm., 1973, 543.
Elements of Group III

111
M-H ct-bond, via the formation of a two-electron, three-centre bond, not
through direct linear hydride-ion transfer.45
The reduction of molybdate ion by NaBH, in acid, neutral, and borate
buffer solutions takes place via the action of BH(OH);, to Mo3+in strongly
acid solution, and to MoO(OH), at pH 2 5.6.4s
Raman spectral data have been obtained in the v(BH) region for BH, in the
following systems :LiBH,, NaBH, in pyridine, isopropyl alcohol, glyme, and
diglyme; NaBH, in H20; LiBH, in Et20, THF. The LiBH,-Et20 system
gave spectra which indicated that a strong interaction (via hydride bridges)
was present between Li+ and BM,. The other systems involved weaker
cation-anion interaction. The LiBH,-diglyme system could only be explained
in terms of a mixture of species.,
Data on the enthalpies of solution of KBH, and LiBH, in 0.011M-NaOH
have been used to calculate the enthalpy of formation of solid KBH, and
LiBH,:
AH;(KBH4, cryst.) = -54.73 & 0.35 kcal mol-I
AH;(LiBH,, cryst) = -44.79 f 0.42 kcal mol-l,
and of BH, in infinitely dilute aqueous solution:

AH;(BH;, soln., co) = 11.00 & 0.36 kcal mol-I.
48
A review has been published on the methods of preparation, properties,

and structures of the tetrahydroborates of Be, Al, Zr, Hf, Th, and U.49
Ab initio calculations suggest that the most stable structure of BeBH, will
be the triply H-bridged system (5). For the known BeB2H, the suggested
(5)
optimum structure possesses a linear or near-linear B-Be-B

skeleton, but
three possibilities seemed to be very similar in energy, (6)-(8), and hence a
high proton mobility is likely.5o
46
G. A. Olah, P. W. Westerman, Y . K. Mo, and G. Klopman, J. Amer. Chem. SOC.,

1972,94, 7859.
46
47
46
V. S. Khain and F. I. Andreev, Russ. J . Inorg. Chem., 1972, 17, 1286.

A. E. Shirk and D. F. Shriver, J . Amer. Chem. SOC.,1973, 95, 5901.
K. N. Semenenko and T. S. Ilina, Rum. J . Inorg. Chem., 1973, 18, 3 .
K. N. Semenenko, 0. V. Kravchenko, and V. B. Polyakova, Russ. Chem. Rev., 1973,
42, 1.
6o
R. Ahlrichs, Chem. Phys. Letters, 1973, 19, 174.
112
The solubility of LiBH4 in ether is increased markedly by the presence of

Mg(BH&, suggesting that some complex formation [giving Mg(BH4)3 or
Mg(BH,)f] is occurring in solution. No complexes could be crystallized out
from the solution, however.51
The systems LiBH,-Al(BH,),-diethyl
ether and LiBH,-Al(BH,),-THF
have been investigated by variable-temperature llB n.m.r. measurements.S2
The equilibrium:
LiBHp
+ AI(BHJ), + LiAl(BH4)4
shifts to the right as the temperature decreases. Further, the complex is more
stable in ether than in THF owing to the more effective competition of the
THF (as a base) for the Lewis acid Al(BH,),. At higher temperatures (ca.
40C) a BH, group exchange is the dominant process, and BH, cleavage
further complicates the investigations in THF solution.
X-Ray data on aluminium borohydride between -60 and -150 "C confirm the existence of two polymorphic modifications. Thermographic
measurements indicate that the compound melts at -64'C, and that
the phase transition occurs at -78 "C. No change takes place in the i.r.
spectrum between -70 and -90 "C,however.53
The vapour-phase i.r. spectrum of U(BH,), is consistent with Td molecular
symmetry, and triple H-bridging, as shown in (9). The solid-phase spectrum
(9)
is more complex, and the nature of the bridging could not be elucidated in
detail.54
Single-crystal neutron diffraction of U(BH,), was more informative in this
respect - showing that each U is surrounded by six BHF ions, four being
terdentate and two bidentate. Thus the U is fourteen-co-ordinate. The space
group is p43212, tetragonal, with a = 7.49, c = 13.24 A; mean interatomic
distances were as follows: r(UH) 2.38(2), r(BH) 1.29(4)
The vapour-phase i.r. spectra of Zr(BH,),, Zr(BD,),, and Hf(BH,),,
together with Raman data on benzene solutions of Zr(BH,), and Hf(BH,),,
are like those for U(BH,)4, i.e. the structure has Td symmetry, with triply
H-bridging units, like (9).66
V. N. Konoplev and V. I. Mikheeva, Doklady Ciiein., 1972, 203, 363.
M. Ehemann, H. Noth, and G. Schmidt-Sudhoff, Z . anorg. Ciiem., 1972, 394, 3 3 .
53 K. N. Semenenko, 0. V. Kravchenko, and E. B. Lobkovskii, J . Struct. Chem., 1972,
13, 508.
54 B. D. James, B. E. Smith, and M. G . H. Wallbridge, J. Mol. Structure, 1972, 14, 327.
55 E. R. Bernstein, W. C. Hamilton, T. A. Keiderling, S . J. La Placa, S. J. Lippard, and
J. J. Mayerle, Inorg. Chem., 1972, 11, 3009.
66 N. Davies, M. G. H. Wallbridge, B. E. Smith, and B. D. James, J.C.S. Dalton, 1973,
51
52
162.

113
Vibrational spectra have also been used to make fairly clear-cut distinctions between unidentate, bidentate, and terdentate H-bridged metal-BH,
interactions for covalent organo-transition-metal or -actinide tetrahydroborates. The following compounds appeared to have bidentate structures :
(h5-C,H5),Ti(BH4), (h5-C5H5),Zr(BH4),,and (h5-C5H5)Zr(H)BH,,while terdentate geometries were applicable for (h5-C,H,),M(BH4) (M = U or Th).57
Kapur et al. have isolated and characterized (h5-C,H5),Ce(BH,) and
(h5-indenyl),Ce(BH,), (from the chlorides NaBH4).58Some i.r. data were
given, but the nature of the Ce-BH, bonding was not deduced in any
detail.
Ab initio calculations have been reported for B2H6and B,H;. For the latter,
it was predicted that the B-H-B
bond should be symmetrical in the gas
phase.59
The new salt [PPh,Me]f[B,H,]- can be isolated from the reaction of
B,H, with [PPh,Me]+[BH,]-. Variable-temperature lH n.m.r. spectra
(between -80 and $1 10 "C) show intramolecular exchange of bridge and
terminal hydrogen atoms at >5OoC. Below ca. -35"C, spin coupling
between these two types of proton was observed ( J H t - H = 5.6 f 0.3 Hz).
llB n.m.r. data were also obtained. BzH; is not attacked by THF, but dimethyl sulphide gives an equilibrium:
Me$
+ BzH; + Me,S,BH, + BHT
llB n.m.r. measurements gave values for the equilibrium constant (in the
range -21 to +31 "C), from which estimates were made of the enthalpy
and entropy of the reaction (AH" = -5.3 f 0.6 kcal mol-l; AS" =
-13.8 f 2.6 e.u.).60
Non-empirical MO calculations on a number of geometries of B3H;
give theoretical support to the pseudorotation mechanism proposed to
account for the equivalence of all the protons on the n.m.r. time-scale.61
B,H,, may be smoothly deprotonated by MeLi at -78OC in diethyl
ether, giving CH,
Li+(B4H9)-. If the latter is reprotonated using DCI,
B4HgDis produced, i.r. evidence indicating the presence of deuterium only
in a bridging position. Li+(B4Hg)-is quite unstable even at -78 "C, and it
decomposes rapidly and irreversibly at higher temperatures. Displacement
reactions suggested the following sequence of Brijnsted acidities : B,H, <
B4H10
< B10H14.62
A number of stable closo- and nido-cobaltoboranes have been prepared

from Na+(B,H,)-. Thus addition of excess CoCI, and Na+C5H, in THF to a
THF solution of Na+(B,H,)- at -196 "C,followed by warming to room
57
58
69
6o
61
62
T. J. Marks, W. J. Kennelly, J. R. Kolb, and L. A. Shimp, Inorg. Chem., 1972,11,2540.

S . Kapur, B. L. Kalsotra, R. K. Multani, and B. D. Jain, J. Inorg. Nuclear Chem.,
1973, 35, 1689.
J. R. Hall jun., D. S. Marynick, and W. N. Lipscomb, Inorg. Chem., 1972, 11, 3126.
R. K. Hertz, H. D. Johnsonjun., and S. G. Shore, Inorg. Chem., 1973, 12, 1875.
P. E. Stevenson, J. Amer. Chem. SOC.,1973, 95, 54.
M. L. Pinsky and A. C. Bond, Inorg. Chem., 1973, 12, 605.
114
temperature, evaporation to dryness, treatment with aqueous HCl, exposure
to air, and extraction with CH2C12,gave a mixture of products. Column
and thin-layer chromatography on silica gel separated the following:
(B,H,)Co(h5-C,H,) [structure (lo)], (1,2-B4H,)Co2(h5-C,H,),, (3-c-C5H,H
(10)
1,2-B4H5)Co,(h5-C,H,),, (4-c-C5H,-1 ,2-B4H5)Co2(h5-C,H,),, and (5-B9HI3)Co(h5-C5H,). Structures were proposed for all of the complexes, which may
be regarded as being derived from formal B4Hz- and B4Ht- l i g a n d ~ . ~ ~
Treatment of 1-MeB,H,, 2-MeB,H8, l-ClB,H,, and 1-BrB,H8 with
K+H- gave rise to deprotonation reactions forming l-MeB,H;, 2-MeB5H;,
1-ClB5H;, and l-BrB,H;. Low-temperature lH n.m.r. studies (-90 to
-130 "C)gave evidence for partial quenching of tautomerism of the bridging
protons in 2-MeB5H7, but not in the 1-substituted anions. llB n.m.r. spectra
indicated that the l-MeB,H; species slowly isomerizes to the 2-isomer.
The following series of relative acidities was proposed: 1-ClB,H8 > B,Hg >
1-MeB5H8 2-MeB,H8.64
The electronic structures of the cage borane anions B,H;--, B,Cl:-, B,,H&,
B1,H\;, and Bl2C1;; have been studied by the SCF-MO method. All valence
electrons were included, and those of the terminal hydrogens also. The closedshell ground-states of these anions were confirmed, although the symmetries
of the highest bonding levels were not the same as previous calculations
had suggested, this being due to the inclusion of the terminal H atoms. In
the borane ions the B atoms bear a formal negative charge, whereas in
the chloro-derivatives it is the chlorine atoms which bear the formal
negative charge.g5
The H- and B,H; ions both react with B5Hg to give, ultimately, the
tetradecahydrononaborate(1 -) ion, B9H; (H- gives a higher yield). B,H,
also reacts with PR, (R = Me or Ph) to give discrete adducts B5H,,2PR,.
llB n.m.r. data were tabulated and assigned for these.66
The reaction of Mn(CO),[B,H,,(THF)] with NEt3 leads to a ring opening
of the THF fragment, with the formation of the zwitterionic Mn(CO),(BgHI2[O(CH2),NEt3]}.67This formulation was confirmed by X-ray crystallography.
63
64
65
66
13'
V. R. Miller and R. N. Grimes, J . Arner. Chem. SOC.,1973, 95, 5078.

V. T. Brice and S. G. Shore, lnorg. Chem., 1973, 12, 309.
D. R. Armstrong, P. G. Perkins, and J. J. P. Stewart, J.C.S. Dalton, 1973, 627.
C. G. Savory and M. G. H. Walibrldge, J.C.S. Dalton, 1973, 179.
D. F. Gaines, J. W. Lott, and J. C. Calabrese, J.C.S. Chem. Comm., 1973, 295.
115
The starting material for the last reaction, together with the parent species
[Mn(CO)3(B91-I13)]-,may be prepared6*by refluxing Mn(CO),Br with BgH;
in THF solution. The crystal structure of the THF adduct was determined,
and its molecular structure is shown in Figure 3.
c (5)
Figure 3 The structure of Mn(CO),[BgH,,(OC,H,)]. Terminal hydrogens on

C(4)-C(7), B(l), andB(3)-B(10) have been omittedfor clarity
(Reproduced by permission from J . Amer. Clzem. Soc., 1973, 95, 3042)
IIB n.m.r. chemical shifts in two series of phenyl-substituted aryldiazoboranes XAr-N,H-B,,H;
(1 1) and XAr-N,-B1,Ht- are linearly related to the
0
, and ( T constants
~
for the substituent groups. These relationships are consistent with a resonance interaction between the two apical positions in the
B,, polyhedron. Inductive and resonance effects may operate in the equatorial
68
3. W. Lott, D. F. Gaines, H. Shenhav, and R. Schaeffer, J . Amer. Chem. SOC.,1973

95, 3042.
116
positions (XAr =I)-CN-, p-Br-, m-MeO-, p-Me-, H-, m-Me-, p-CF,-,

m-F-, m-Br-, p-F-, m-CF,-, and p-MeO-C,H4-).6g
The BloH:; ion has two BH, groups and two bridging H atoms in a 2632
topology of three-centre-bond theory. The isolated ion possesses C2, symmetry (12), while the NMez salt crystallizes in the space group P2,/c, with
u = 9.60(1), 6 = 16.29(1), c = 12.27(1) .$; /? = 91.63(1)'; a n d 2 = 4.70
H
(12)
The llB n.m.r. spectrum (70.6 MHz) of BloH; consists of 4 doublets, of

relative intensities 4:2:2:2. These are assigned to B(5,7,8,10), B(1,3 or 2,4),
B(2,4 or 1,3), and B(6,9), respectively. The 220 MHz lH n.m.r. spectrum of
this anion consists of a low-field set of peaks and an upfield broad, symmetrical peak (relative intensities 10:5). There appear to be 5 bridging H
atoms in BloHG, probably undergoing rapid exchange in solution at room
temperature. Possible structures are drawn in Figure 4 (a), (b), and ( c ) . ~ ~
The B,,,Hi; and B1,H7Bri- ions have been shown to behave as fluxional
molecules at low temperatures, by studying IlB n.m.r. spectra, with IH
decoupling, in the range -70 to +30 "C. A mechanism involving the interconversion of two C,,isomers was proposed.72
A direct synthesis of dialkyl sulphide derivatives of Bl2H;; has been
reported,73 using dimethyl sulphoxide and acetic anhydride, thus :
Me,SO
+ -(MeCO),O -+ Me2SOCOMe+ + MeCOO+ B12H2,, -+ B12HllSMeL + MeC0,H
Me,SOCOMe+
Further reaction yields the bis-dialkyl sulphide derivative.

n- or i-Bl,Hg; react with numerous phosphine- and carbonyl-substituted
complexes of Co, Rh, Ni, Pd, and Pt to give new metal-borane complexes
69
70
71
72
73
A. R. Siedle and G. M. Bodner, Znorg. Chem., 1973, 12, 2091.

D.S. Kendall and W. N. Lipscomb, Inorg. Chem., 1973, 12, 546.
R. R. Reitz, A. R. Seidle, R. Schaeffer, and L. J. Todd, Znorg. Chem., 1973, 12,2100.
E.I. Tolpin and W. N. Lipscomb, J. Amer. Chem. Soc., 1973, 95, 2384.
J. Wright and A. Kaczmarczyk, Znorg. Chem., 1973, 12, 1453.
117
0
(a1
Figure 4 Possible structures for the BlOHG ion in solution

(Reproduced by permission from Inorg. Chem., 1973,12,2100)
[(B18H20)M(ligand)n].74
The proposed structure of [(n-B18H20)Ni(PPh3)2]
is shown in (13; L = PPh,). The reaction of i - B & & with cyclohexyl isocyanide gives the carbaborane B1,H2,,CNH2C6Hl,.
Carbaboranes and their Metal Derivatives.-Matteson

has written a comprehensive review of the literature on carbaboranes for the year 1972.75
Hawthorne and co-workers have reviewed the chemistry of non-icosahedral
c a r b a b o r a n e ~and
~ ~ of metall~carbaboranes.~~~~~
The general polyhedral expansion method has been used to produce a large
number of new metallocarbaborane~.~~
Thus, reduction of the closo-carbaboranes l,7-C2B6H,,4,5-C2B7H9,1,6-C2B8H,,, 1,10-C2B8Hl0,and2,3-C2B9Hll
with Na, followed by treatment with CoCI, and NaC,H5, produces (h5-C5H5)c o (C,BnHn+z)
(h5-c5H5)c012 (C2BnHq-2) and (h5-C,H5)COC~BnHn+l'
(C2B,H,+,). In addition, treatment of the anions derived from the reduction
of 1,7-C,B,H8 and 1,6-C2B8Hl, gives new ferracarbaboranes. All of the
9
74
7s
76
77
78
7*
R. L. Sneath and L. J. Todd, Inorg. Chem., 1973,12,44.

D. S. Matteson, J. Organometallic Chem., 1973, 58, 1.
G. B. Dunks and M. F. Hawthorne, Accounts Chem. Res., 1973, 6 , 124.
M. F. Hawthorne and G. B. Dunks, Science, 1972,178,462.
M. F. Hawthorne, Pure. Appl. Chem., 1973,33,475.
W. J. Evans, G. B. Dunks, and M. F. Hawthorne, J . Amer. Chem. SOC.,1973,95,4565.
118
metallocarbaboranes produced were characterized in the usual way and

structures proposed. Those for [(~5-C,H5)Co]2(C2B6H,)(14), (h5-C5H5)CoC,B,H,(C,B,H,) (15 ) , and (h5-C5H5)Fe(C,B6H,)(16 ) are shown.
An ab initio and semi-empirical MO study of the closo-carbaboranes
1 ,5-C,B,H5, 1,2-C2B4H6,1,6-C,B4H6, and 2,4-C2B5H, has been carried
out.80 The delocalized MO's from both types of calculation can be transformed into localized orbitals to provide an analysis of the multi-centre
bonding in these molecules which requires no prior assumptions about the
nature of the bonding.
80
M. F. Guest and I. H. Hillier, Mol. Phys., 1973, 26,435.
119
I
1
I
H
(15)
Gas-phase electron-diffraction studies on 1,5-dicarba-cZoso-pentaborane

and 1,6-dicarba-cZoso-hexaboranehave been reported.*l They possess DSh,
DPhsymmetry, respectively, in the gas phase. The carbon atoms are located at
apical positions and may be regarded as being bonded to rings of three or
four equivalent boron atoms. The following molecular dimensions were
derived: 1,5-dicarba-cZoso-pentaborane:r(BC) 1.556, r@B) 1.853, r(CH)
1.071, r(BH) 1.183 A; LBCC 73.05', LCBB 53.48", LCBC 93.16'. The
II
81
E. A. McNeill, K. L. Gallaher, F. R. Scholer, and S. H. Bauer, Inorg. Chern., 1973,12,

2108.
1 20
distance from the carbon atom to the boron 'belt' is 1.131 A. 1,6-Dicarbacloso-hexaborane: r(BC) 1.633, r(BB) 1.720; r(CH) 1.103, r(BH) 1.244 A;
LB(2)CB(3) 63.56', LCBB 58.22', LCBC 83.73", LB(2)CB(4) 96.26'.
The distance from the carbon atom to the boron 'belt' is 1.090 A.
9
I
I
I
I
co
I
'Triple-decker' sandwich compounds [ e g . (17)] have been prepared and

characterized which contain the planar C2B3Ht- ligand, analogous to C,H; .82
For example :
The negative-ion mass spectra of the small closo-carbaboranes 1,5-C2B3Hs,

1,2-C2B4H6,1,6-C2B4H6,and 2,4-C,B5H7 show much more intense (P - 1)
ions than parent ions, this being related to the ease of formation of conjugate-base anions of these cage compounds. Ionization-efficiency diagrams
indicate that negative ions of doso-carbaboranes are formed with more
difficulty than those of nido-carbaboranes, reflecting the lack of bridging
hydrogen atoms in the former.83
Negative-ion mass spectra of 2,3-dicarbahexaborane(8), 2-methyl-nido2,3-dicarbahexaborane(8), and 2,3-dimethyl-nido-2,3-dicarbahexaborane(8)
82
83
D. C. Beer, V. R. Miller, L. G . Sneddon, R. N. Grimes, M. Mathew, and G. J.

Palenik, J. Amer. Chem. SOC.,
1973, 95, 3046.
T. Onak, J. Howard, and C. Brown, J.C.S. Dalton, 1973, 76.
121
show that formation of negative ions in these nido-carbaboranesoccurs primarily via resonance-capture and dissociative resonance-capture rnechanisrn~.~~
A calculation of localized MOs for the 1,2- and 1,6-C,B,H6 molecules has
been made.85 For the 1,6-isomer, the LMO structure is best interpreted in
terms of fractional three-centre bonding, but for 1,2-C,B4H6
an open threecentre bond appears to be necessary. This is the first example of such a bond,
and it means that the three-centre-bond theory must be extended to allow for
this, especially when carbon is the central atom.
Minimum-basis-set SCF wavefunctions have been calculated for 4,5dicarbahexaborane(8) (1 8).8s
A Russian group has determined the molecular structure of lY6-dicarbacloso-hexaborane(6) (19) by electron d i f f r a c t i ~ nThe
. ~ ~ molecular dimensions
were in good accord with those reported by McNeill et aL81
C(4)H
(18)
The reaction of 1,6-dicarba-closo-hexaborane(6) with NMe, produces a

f
new carbaborane, formulated as 5-M%N- [2,4-C2B4H6]-,i.e. as a zwitterion.

This is a thermally stable white solid, soluble in polar but not in non-polar
solvents. llB n.m.r. spectra are consistent with the structure (20).88
The compounds ,u-Me3M-C,B,H7 (M = Sn or Pb) have been prepared and
A number of their reactions were studied which revealed
characteri~ed.~~
considerable differences between them and the previously prepared Si and Ge
analogues. For example, the new species fail to show thermal rearrangements
to terminally-substituted isomers which are characteristic of the Si and Ge
species.
C. L. Brown, K. P. Gross, and T. Onak, J. Amer. Chem. SOC.,1972,94, 8055.
I. R. Epstein, D. S. Marynick, and W. N. Lipscomb, J. Amer. Chem. SOC.,1973, 95,
1760.
ST
D. S. Marynick and W. N. Lipscomb, J. Amer. Chem. SOC.,1972, 94, 8699.

V. S. Mastryukov, 0. V. Dorofeeva, L. V. Vilkov, A. F. Zhigach, V. T. Laptev, and
A. B. Petrunin, J.C.S. Chem. Comm., 1973, 276.
B. Lockman and T. Onak, J. Amer. Chem. SOC.,1972, 94, 7923.
A. Tabereaux and R. N. Grimes, Inorg. Chem., 1973, 12,792.
122
-NMe
Me
Al,I,-catalysed iodination of C,B,H, produces a mixture of 3-I- and 6-IC2B4H,,with none of the l-iodo-is~mer.~~
Some new iron-carbaborane complexes have been prepared by Sneddon
and Grimes :91
+ NaH -+Na+[C2B4H7]-+ H,
2,3-C2B4Hs
Na+[C,B4H71-
+ [(h5-C5H5)Fe(CO),I]--+
-NaI
25
O C
,u-[(h5-C5H5)Fe(C0),lC2B4H7
,u-[(h5-C5H5)Fe(C0),]C2B4H,
5 (h5-C5H5)Fe11(~-C2B4H,)
-2co
(22)
+ (h5-C5H5)Fe1I1(r-C2B4H6)
(23)
N.m.r. spectra are consistent with the structures shown, (21)-(23),

last-named is paramagnetic.
91
T. J. Reilly and A. B. Burg, Inorg. Chem., 1973, 12, 1480.

L. G. Sneddon and R. N. Grimes, J. Amer. Chem. SOC.,1972,94,7161.
and the
123
A series of new cobaIt(III)-small carbaborane sandwich complexes has

been prepared from closo-C,B,H, via reduction with sodium naphthalide in
THF, followed by reaction with CoCI, and Na+C5H; and aerial oxidation.92
The compounds are : (rr-C2B,H,)Co(h5-C5H5), (rr-C2B5H,)Co(h5-C5H,),
(T-C2B6H&O (h5-C5H5),(rr-C,B,H6)C0,(h5-C5H5),, (rr-C2B5H,)Co,(h5-C,H5),,
(~-C,B,H8)Co,(h5-C5H,),, [rr-(a-C2B5H,)C2B,H5]Co(h5-C5H,),
and [T-(oC,,H,)C2B,H5]Co(h5-C5H5). Characterization was based upon llB and lH
n.m.r., i.r., and high-resolution mass spectra. The formal C,B,Hp, C,B,Hk,
and C,B,H;- ligands are new, while the C2B4H:-, C&,Hi-, and C,B,Htligands are new structural isomers of previously reported ligands.
C(7)H3
C(8)HS
(24)
Gas-phase electron-diffraction measurements on hexamethyltetracarbahe~aborane(6)~~

(24) have yielded the following structural parameters :
C(l)-C(2)
C(2)-B(3)
83
1.436, C(l)-C(5)
1.755, C(2)-B(6)
1.452, C(l)-B(6) 1.534, C(l)-C(S)

1.447, B(3)-B(6) 1.719, B(3)-C(10)
V. R. Miller and R. N. Grimes, J. Amer. Chem. SOC.,1973, 95, 2830.

J. Haase, 2.Naturforsch., 1973, 28a, 785.
1.592,
1.472,
124
B(6)-C(7) 1.264 A; LC(S)B(l)B(6) 61.7', LC(S)C(l)C(8) 132.3', LC(8)C(l)B(6) 170.7', LC(2)C(l)B(6) 58.2', LC(2)C(l)C(8) 123.0", LC(l)C(2)B(6)
64.3', LC(3)C(2)B(6) 64.lo, LC(l)C(2)C(9) 116.4' , LC(3)C(2)C(9)
119.8' , LC(9)C(2)B(6) 168.4' , LC(2)B(3)B(6) 49.3' , LC (1O)B(3)B(6)
170.6', LC(2)B(3)C( 10) 125.6' L C(2)B(3)C(4) 81Soy L C(1)B(6)C(7)
122.7', LC(2)B(6)C(7) 125.0', LB(3)B(6)C(7) 110.Oo, LC(l)B(6)C(5) 56.5',
L C (l)B(6)C(2) 57.5', LC (2)B(6)B (3) 63.5'.
A minimum-basis-set SCF wavefunction of 2,4-dicarbaheptaborane(7) (25)
has been c a l ~ u l a t e dA
. ~number
~
of molecular parameters were calculated and
H
H'
'
(25)
the reactivity of the molecule was discussed in terms of ground-state charge

distribution. B(3) appears to be participating in five bonds to other atoms,
and these fractional bonds were discussed in terms of their directional
character, hydridization, and percentage delocalization.
A new polyhedral contraction reaction involving the loss of three BH and

one CH units produces the complex [(h5-C5H5)C~11r(rr-2-B,CH8)](26) :
reflux
(h5-C~H6)CoII1(~-6,7-B~~C~H~2)
KOH 4
Et O H
K+[(h6-CsHs)C~"'(~-2-B
,CH a)]Q4
D. S . Marynick and W. N. Lipscomb, J. Amer. Chem. SOC.,1972, 94, 8692.
125
The proposed structure is based upon analysis of lH and llB n.m.r. data.95*96
A polyhedral expansion reaction has been used97to produce a new binietallic mixed metal monocarbon metalloborane :
Na+C,H;
+ NiBr,,2C2H4(OMe), + [Me4N][(h5-C5H5)Co1*I(~-B,CH8)]
--t
(hW,H,)Co II1(?r-B,CH,)NiIV(h5-C,H5)
This can be isolated in at least 4 isomeric forms, one of which, (27), is

illustrated.
Passing 5 ,6-C,BsH,, through an evacuated tube at 500 O C gives a mixture of

1,6-dicarba-closo-decaborane(lO)and 1,lo-dicarba-closo-decaborane(l0). At
200 O C , the sodium salt of the anion of the initial compound disproportionates, thus:98
2(5,6-C,B8H,1) + Ha
+ l,ZCtB&Ilo + CaB8H:;
Base degradation of [LCo(v-(3)-1,2-BgC,H,1)]z, followed by oxidation,

effects a polyhedral contraction to [LCo{n-(1)-2,4-BsC,H10}]"
(28), where
I-
L
I
H
(28)
95
gs
97
ng
D. F. Dustin and M. F. Hawthorne, J.C.S. Chem. Comm., 1972, 1329.

D. F. Dustin and M. F. Hawthorne, Inorg. Chern., 1973,12, 1280.
C. G. Salentine and M. F. Hawthorne, J.C.S. Chem. Comm.,1973, 560.
B. Stibr, J. PleSek, and S. Hefmhek, Coll. Czech. Chem. Comm., 1973,38, 3 3 8 .
126

L = C5H;, z = 0 or L = (3)-ly2-BsC2H:;y z = -1. Subsequent degradation of these, using FeCl,, gave [(h5-C5H,)Co(7r-B7C2HI1)](29) and
H
[{r-(3)-1,2-B,C2H,,)Co(n-B,C,H,)]- (30). The former complex eliminates

H, at 150 "C to give [(h5-C5H5)Co{~-(2)-1
,10-B7C,H,)] (31). The structures
illustrated were proposed on the basis of mass spectra and llB n.m.r. spectra.s9
I
I
yo
I
I
I
I
I
I
I
To
I
An organoborane anion, (C,H,),B,H;,

(32), has been preparedloo in
which there is a single transannular hydrogen bridge. The structure was
confirmed by X-ray crystallography, which gave B-Hbridge distances of 1.28
and 1.31 A.
C . J. Jones, M. F. Francis, and M. F. Hawthorne,J. Amer. Chern. Soc., 1972,94,8391.
W. R. Clayton, D. J. Saturnino, P. W. R. Corfield, and S. G. Shore, J.C.S. Chem.
Comm., 1973,317.
loo
127
(32)
A new carbaborane isomer, 2,9-dicarba-nido-undecaborane(l3), 2,9C2BgHl3,has been preparedlOl by the alkaline solvolysis of 1,12-dicarbacZoso-dodecaborane(l2), followed by acidification of the resulting 2,9dicarba-nido-dodecahydroundecaborate(1-) ion. It is stable to water and
air, forms colourless crystals, and its spectroscopic properties are consistent
with the structure (33). It is suggested that the stability of this compound and
H
(33)
of the known 7,s-isomer is related to the fact that both bridging hydrogens
can be accommodated adjacent to the open face of the molecule. This is not
possible for the so-far unknown 7,9-isomer.
1 ,S-(CH3)2C2BgHg
reacts with chromic acid in benzene at 0 OC to give a
(numbering as in
bis(hydroxy) derivative [1,8-(3,7)-(CH3),C2BgH,(OH),]
Figure 5 ) - the structure of which is in agreement with spectral and chemical
evidence for the presence of two hydroxy-groups in adjacent positions, on
B(3) and B(7). On pyrolysis, the bis(hydroxy)-compound dimerizes to give
(34).102
(34)
Io1 J. Plegek and S. Hei.mAnek, Chem. and Ind., 1973, 381.
loa G. D. Mercer and F. R. Scholer, Inorg. Chem., 1973, 12,
2102.
I28
e.8-H
UD :C-CH3
@=B-Oti
Figure 5 Numbering system and proposed structure for I ,8-dimethyl- (3,7)dihydroxy-l,8-dicarba-closo-undecaborane(

1 1)
(Reproduced by permission from Iizorg. Chem., 1973, 12,2102)
The reaction of GeI, with 7,9-BsC2Ht, leads to the formation of 3-Ge-1,7BsC,Hll (35). If SnC1, is used as reagent, however, the 3-Sn analogue is not
produced ; oxidative closure of the anion occurs instead, giving high yields of
2,3-BsC,Hll. If this is subsequently treated with a ligand L (NMe,, PPh,, or

OEt-), then 3-L-7,9-BsC2Hll is formed. These adducts were characterized by
i.r., llB n.m.r., and mass spectra.lo3
The molecular structure of Et,Nf[(B,C,Hll)Co(B8C2Hlopy)]has been
determinedlo* by a complete three-dimensional X-ray diffraction study.
The CoTrl atom is sandwiched between mutually staggered B,C2H:, and
B,C2Hlopyz ions (Figure 6). The B8C, skeleton of the latter defines an
icosahedron from which two adjacent apices have been removed.
Two reportslo5*lo6
have been made of the preparation of (h5-C,H,)M{n-(3)1 ,2-B9C2Hl1)(M = Fe or Co) and of [((h5-C,H,)Co)2{rr-(3,6,2-B8C2Hlo)]
)-1
lo3
V. Chowdhry, W. R. Pretzer, D. N. Rai, and R. W. Rudolph, J . Amer. Chem. SOC.,

1913,95,4560.
M. R. Churchill and K. Gold, Inorg. Chem., 1973, 12, 1157.

J. PleSek, B. Stibr, and S. Heimbnek, Synth. Inorg. Metal-org. Chem., 1973, 3 , 291.
lo6C. J. Jones and M. F. Hawthorne, Inorg. Chem., 1973, 12, 608.
lo*
lo5
129

P'Y(21
Figure 6 Molecular structure of the [(BgC2Hll)Co(B8C2H~~py)lion

(Reproduced by permission froin Inorg. Chem., 1973, 12,1157)
(36) by the reaction of MC12, C,H,, and ethanolic KOH on K+[(3)-1,2BgC2H12]-.The first complex (for M = Co) reacted with Co'II in the presence
of OH- to give the trimetallic species [{(h5-C5H,)Co[~-(3,6)-1
,2B,C2H10] )~CO]-(37).lo6
The crystal and molecular structures of tetramethylammonium 3,3'-cornrnobis-l,2-dicarba-3-nickela-cZuso-dodecaborate(
1 -) have been determined.lo7
The unit cell is orthorhombic (space group Ccmm; a = 10.328, b = 9.841,
c = 21.86 A; 2 = 4). The anion [Ni(C,BgH,,),]has a symmetrical vsandwich type of structure, Figure 7, with two dicarbollyl icosahedra joined
at the Ni apex.
A new method has been reported for the preparation of claso-metallocarbaboranes, using the novel thallium(1) derivative T1+[TlR1R2C2BgH,]- (R1,
lo'
F. V. Hansen, R. G. Hazell, C. Hyatt, and G. D. Stucky, Acta Chem. Scand., 1973,27,

1210.
130
(37)
t
@
Ni
Figure 7 Molecular structure of the anion [Ni(C2BgH1J2](Reproduced by permission from Acta Chem. Scand, 1973,27,1210)
131
R2 = H, Me). This, on treatment with FeCI,, CoCI,, [Pt(l,5-C8H12)CI,],

or cis-[Pd(PPh,),CI,], gives high yields of the corresponding 7r-(3)-1,2dicarbollyl derivatives. Also, closo-1,8-Me,C2B,Hg reacts directly with a
number of d10 complexes of Ni, Pd, and Pt to give, for example, (38), in
PhaP,
\
,PPh,
r
which the metal occupies the vacant icosahedral site above a nido-1,7-Me2C,B,Hg fragment.los
The photochemical reaction of 7,8-BgHloCHP- and 7,9-BgHloCHP
with Fe(CO), and Mn,(CO)lo gives complexes in which the phosphacarbaborane ligand has replaced a CO group, giving a-bonded transition-metal
complexes.10s
A sealed-tube pyrolysis of BMe, yields 25 % of a compound (BMe),(CH),.
N.m.r. spectra are consistent with the presence of 6 equivalent BMe and 4
equivalent CH groups. Hence an adamantane-like structure (39) was proposed for the cage.l1
The electrochemistry and 80.5 MHz llB n.m.r. spectra of the monocarbon
carbaboranes Bl1CHF2, BloCH;l, and Bl0CH;, have been investigated.lll
lo8 J. C. Spencer, M. Green, and F. G. A. Stone, J.C.S. Chem. Comm., 1972, 1178.
lo9 D. C. Beer and L. J. Todd, J. Organometaliic Chem., 1973, 55, 363.
110 M. P. Brown, A. K. Holliday, and G. M. Way, J.C.S. Chem. Comm., 1973, 532.
ll1 R. J. Wiersema and M. F. Hawthorne, Inorg. Chem., 1973, 12, 785.
10
132
(40)
The last undergoes a one-electron oxidation to give B,,C,H;; (40) in high

yield. The n.m.r. spectrum of BloCH& is inconsistent with previously proposed structures, although it may be rationalized in terms of the rapidly
interconverting structures shown in Figure 8.
Oxidation of the cobalt complexes obtained from o-, m-,or p-C,Bl,H;;,2
and CoCl, leads to mixtures of the o-, m-, andp-carbaborane(l2) isomers in
8 CH
0BH
Figure 8 Apossible sequence of rearrangementsfor the ion BloCHG

ratios depending upon the temperature of the reaction.l12 The activation

energies for isomerization in the complexes are clearly less than those for
uncomplexed C2BloHi; ions, where isomerization is not observed, even at
temperatures as high as 150 'C.
The isomeric o-, m-, and p-carbaboranes and their Et,Sn derivatives have
been examined by lH-(llBI heteronuclear magnetic resonance techniques to
obtain accurate proton chemical-shift and coupling-constant data.l13
Dipole moments of isomeric icosahedral monobromo-o-carbaboranes have
been measured: l-Br 3.34 D, 3-Br 3.69 D, 4-Br 4.47 D, 8-Br 5.48 D, 9-Br
5.98 D.l14
Bromine-substituted 1,2-dicarba-cZoso-dodecaboranes behave as Lewis
acids, and with pyridine give compounds formulated as 3,6-dipyridine-l,2dicarba-closo-dodecaboranes (isoelectronic with C2Bl,Hf;).115 No such
113
114
V. A. Brattsev and V. I. Stanko, J. Organometallic Chem., 1973, 55, 205.

A. P. Tupchauskas, V. I. Stanko, Yu. A. Ustynyuk, and V. V. Khrapov, J . Struct.
Chem., 1912, 13,112.
V. Gregor, V. JehliEka, and J. Stuchlik, Coll. Czech. Chem. Comm., 1972, 37, 3859.
J. PleSek, T. Hanzlik, F. Hanousek, and S. Heimanek, Coll. Czech. Chem. Comm.,
1972, 37, 3403.
133
reactions of unsubstituted 1,2-dicarba-cZoso-dodecaboranewith Lewis bases

were found.
A mixture of 1,9- and 1,2-dibromo-1,2-dicarba-cZoso-dodecaboranemay
be obtained (a) by direct bromination (using Br, AlBr,) of the l-bromoderivative, or (b) by treatment of the 9-bromo-derivative with RMgX,
followed by Br,.l16
Solid-state fluorination (using F,) of m-carbaborane can yield the perfluoro-rn-carbaborane in a one-stage process.l17
o-, m-, and p-carbaboranes and their derivatives can be 'silylalkylated'
by chlorovinylsilanesand alkylchlorovinylsilanes in the presence of aluminium
chloride. Reaction takes place at a B-H bond, according to the equation1l8:
HCBl,HloCH 3. HaC==CHSiCl,--f HCBloH,o-,(CH2CH2SiC13)nCH
(where n = 1-3).
A maximum of three equivalents of sodium can add to l-(halogenomethy1)o-carbaboranes in liquid ammonia solution. Hydrolysis of the anions so
produced followed by permanganate oxidation gives, unexpectedly, up to
15 % of the l-methyl-m-~arbaborane.~~~
Apparently during the sodiumammonia reduction there is a change in the icosahedral structure.
Triethylgermylmercury derivatives of 1,2- and 1,7-dicarba-closo-dodecaborane(l2) may be synthesized using exchange reactions of Hg(GeEt,),
with mercury compounds of the types Hg(CBloH,,CR), or R1HgCBloHloCR2
(R1= CI, Me, or Ph; R2 = H, Me, CH,Cl, or Ph).lZo
The syntheses of 2-carboxy-, 2-amino-, and 2-hydroxy-derivatives of 1,7dicarba-closo-dodecaboranes have been reported.121 All were produced in
good yields by simple routes from2-vinyl-l,7-dicarba-closo-dodecaborane(
12),
which was itself prepared by the reaction of vinylboron dichloride with the
dilithium salt of undecahydrido-7,9-dicarba-nido-undecaborate(2-).
Single-crystal X-ray diffraction studies on NMet [PhCHBloH1,CPh]show that in the anion there is a unique bridging carbon atom of the PhCH
group on the face of an icosahedral Bloc fragment. There are no bridging
hydrogens. The structure is shown in (41), which omits the terminal B-H
hydrogens, and only the bonding C atom of each phenyl ring is shown.122
rn-Carbaboran-l-yl-phosphorousand -phosphoric acids can be prepared
from the lithium derivative m-HCBloH,,CLi and PC1(NEt2),.123
116
11'
11*
119
120
lZ1
12a
123
J. PleSek and T. Hanzlik, Call. Czech. Chem. Comm., 1973, 38, 335.
R. J. Lagow and J. L. Margrave, J . Inorg. Nuclear Chem., 1973,35,2084.
V. F. Mironov, V. I. Grigos, S. Ya. Pechurina, and A. F. Zhigach, J. Gen. Chem.
(U.S.S.R.), 1972, 42, 2577.
V. I. Stanko, Yu. V. Gol'tyapin, and N. S. Titova, J. Gen. Chem., (U.S.S.R.),1973,43,
214.
0. A. Kruglaya, L. I. Zakharkin, B. I. Petrov, G. S. Kalinina, and N. S. Vyazankin,
Synth. Inorg. Metal-org. Chem., 1973, 3 , 63.
L. I. Zakharkin, V. N. Kalinin, and V. V. Gedymin, Synth. Inorg. Metal-org. Chem.,
1973,3, 93.
E. I. Tolpin and W. N. Lipscomb, J.C.S. Chem. Comm., 1973, 257.
A. V. Kazantsev, M. N. Zhubekova, and L. I. Zakharkin, J. Gen. Chem. (U.S.S.R.),
1972, 42, 1561.
134
The reaction between Me3N,BH21 and Li+[l ,2-BloC2Hll]- or Li+[l,7BloC,Hll]- leads to the isomeric trimethylamine carbaboranyl boranes
1-Me,N,BH2-1,2- and 1-Me,N,BH2-1,7-B10C2Hll,re~pective1y.l~~
These are
rather resistant to degradation by acids or bases (except piperidine). Characterization was achieved by lH and IIB n.m.r., Lr., and mass spectroscopy.
The isomeric 1,2-, 1,7-, and 1 ,12-B1&,H12 carbaboranes and some of their
derivatives can be reduced with Na to give BloC2Hf; ions, which can be
protonated to yield (13)-9,11-B1,C2H;, (42), (13)-7,10-BloC2H~,and some
derivatives (43). Pyrolysis of Me4N+[(13)-7,10-BloC2H13]- gave Me3NBH,1,2-B1,C2Hll (44) together with Me4N+[(12)-7,9-BsC2H12]-.126
Treatment of the disodium salts of 7,8- and 7,9-BgHgCHE2-(E = P or As)

with GeI, in refluxing benzene results in the formation of 1,2,3- and 1,2,7GeB,H,CHE, icosahedral boranes containing three different hetero-atoms in
the cage. The structures were deduced by the usual spectroscopic techniques,
and that for the 1,2,3-isomer is shown in (45). The 1,2,7-isorner is thermally
la4
125
D. N. Rai, C. R. Venkatachelam, and R. W. Rudolph, Synth. Inorg. Metal-org. Chem.,

1973, 3, 129.
G. B. Dunks, R. J. Wiersema, and M. F. Hawthorne, J . Amer. Chem. Soc., 1973,95,
3 174.
135
(44)
(45)
more stable than the 1,2,3-one. This may be rationalized in terms of the
greater charge separation in the former.126
The first report of the oxidative addition reaction of Ir with a B-H bond
of a complexed carbaboranylphosphine has appeared.12' The reaction scheme
is shown in Figure 9, and the attack at a B-H and not a C-H bond was
substantiated by the use of isotopically (H and D) substituted carbaborane
derivatives.
A
-cyclohexane
2
7
Mc'
12
Figure 9
(Reproduced by permission from J. Arner. Chem. SOC.,1973, 95, 2712)
126
12'
D. C. Beer and L. J. Todd, J. Organometallic Chem., 1973, 50, 93.

E. L. Hoe1 and M. F. Hawthorne, J . Amer. Chem. SOC.,1973,95,2712.
136
co
M'
(47)
(48)
1,2-Dicarba-cZoso-dodecaborane(12) undergoes a two-electron reduction with Na in THF to give BloC2H$.128 This ion serves as a ligand in
the formation of a number of transition-metal complexes, e.g. [(h5-C,H,)~(~-13~oC212)l
(M = FerI1 or ColIr) (46), [(~-BloC2Hl.-J2M'ln- (M' =
CorT1,FerI1,or Nirr) (47),and [(.rr-BloC2H12)M"(CO),]2(M" = Mo or W)
(48). The structures all contain closo-polyhedra, with the metal atom located
at one of the 13 vertices.
D. F. Dustin, G . B. Dunks, and M. F. Hawthorne,J. Arner. Chem. Soc., 1973,95,1109.
137
X-Ray structural analysis shows that (h5-C5H5)Co

(~-7,9-BloC2H12)
contains a 13-vertex docosahedron in which an apical ColI1 atom is linked
directly to a six-atom B4C, face, Figure 10. The docosahedron possesses a
very irregular geometry.12g
Figure 10 Molecular structure of (h5-C6H5)Co(7r-7,9-BloC2H12)

(Reproduced from J. C. S. Chern. Comm., 1972, 1326)
The crystal structure of C O [ ( B ~ ~ C ~ H ~(as

~ ) the
~ ] ; Et4N+ salt) has been
determined; it belongs to the monoclinic space groupP2,/c,with a = 14.85(1),
b = 18.66(2), c = 15.54(1) A, = 95.6(1)'J3O Four carbaborane icosahedra
are arranged tetrahedrally about the Co, but the carbons bonded to the Co
are distorted from regular tetrahedral geometry, while there is also a B-HCo bridging interaction (49), the Co-H distance being 1.82 A.
The vibrational spectra of the phosphorus and arsenic carbaboranes

Bl0H1,PCH and B,,H,,AsCH (1,2-, 1,7-,and 1,12-isomers) have been
reported.131Only the v(CH) band was assigned in each case.
Ethynyldicarbadodecaborane(l2) reacts with trans-[IrCl(CO)(PPh,),] to
An X-ray
give the 2: 1 adduct [IrCl(CO)(PPh3),J,(B10C4H11)(B10C4H13).
I3O
131
M. R. Churchill and B. G. De Boer, J.C.S. Chem. Comm.,1972, 1326.

R. A. Love and R. Bau, J . Amer. Chem. SOC.,1972,94, 8274.
L. E. Vinogradova, V. I. Kyskin, L. A. Leites, and L. I. Zakharkin, Bull. Acad. Sci.
U.S.S.R., Div. Chem. Sci., 1972,2372.
138
om
Figure 11 Molecular structure of IrCl (CO)(PPh,), (B10C4H11)(Bl0C4HI3).
Phenylgrocps have been omittedfor clarity. Bond IengthslA
(Reproduced from J .C.S.Chem. Comm., 1973,465)
crystallographic study showed132that this contained a o-2-carbaboranylacetylide and a o-trans-2-carbaboranylvinylsubstituent ,Figure 11.
Careful oxidation of C 2 B , H ~by KCr,O, in an acidic medium at - 15 "C
yields the new stable carbaborane C4B1,H,,. N.m.r., Lr., and mass spectral
data could not give an unambiguous decision concerning the structure, but
133
K. P. Callahan, C. E. Strouse, S. W. Layten, and M. F. Hawthorne, J.C.S. Chem.

Comm., 1973,465.

139
where 0 = BH,
one of the possibilities shown in (50) must be
@ = B, = C , and a = BH or CH.
An improved synthesis has been reported134 for the biscarbaborane
( 5 1)
compound (5 l), which is 1- [1-1,2-dicarba-cZoso-dodecaborane(12)]-1,2dicarba-doso-dodecaborane( 12) :
2@10H12,2SEt2)
+ HCkC-CH
toluene
-25
oc
heat
+
(51)
aooc
+ 2H2
lH n.m.r. measurements on glassy polymers containing 1,2- or lY7-diphenylcarbaborane units in the chain indicate that there is a considerable amount of
molecular mobility - this rather surprising result is explained by the effect of
the bulky carbaborane groups in disrupting the polymer structure.135
Polymerization of 1-vinyl-o-carbaborane proceeds primarily via a freeradical intermediate.136
Temperature-dependent effects in the lH n.m.r. spectrum of the l-vinyl-ocarbaborane radiolysis polymer can be interpreted in terms of a spin-relaxation mechanism of deco~p1ing.l~~
The dynamics of formation of this polymer
under the influence of 6oCo y-rays have been investigated, and E, for the
propagating step of the process has been estimated13*as 3.3 kcal mol-l.
Aminoboranes and other Compounds containing B-N Bonds. Ab initio
Aculations have been performed on the lC+ ground state of an isolated
BN molecule, using basis sets of 22, 32, and 48 Gaussian functions. The
equilibrium internuclear distance and total electronic energy obtained using
the largest basis set were 2.35 bohr and -78.8580 hartree, respe~tive1y.l~~
1.r. spectra of the 1216 photolysis product of ammonia-borane H3NBH3
in rare-gas matrices suggest that the major product is imidoborane, HNBH.
Two of the three Z+vibrations for this linear system are at 3700 cm-l (vl),
1785 cm-l (v3), respectively, (for llB, 14N species in an argon matrix).
v 2 was calculated to be at 2800 cm-l, while one of the bending modes was
observed at 460 cm-l. Prolonged photolysis produced some HNB also
133
134
135
136
lS7
138
139
J. Plegek and S. HePminek, Chem. and Ind., 1972, 890.

T. E. Paxson, K. P. Callahan, and M. F. Hawthorne, Inorg. Chem., 1973, 12, 708.
V. S. Matochkin, A. I. Kalachev, Yu. V. Zelenev, P. M. Valetskii, S. M. Vinogradova,
and V. V. Korshak, Doklady. Chem., 1972,304,532.
T. J. Klingen and J. R. Wright, J . Inorg. Nuclear Chem., 1973, 35, 1451.
J. R. Wright and T. J. Klingen, J. Inorg. Nuclear Chem., 1972, 34, 3284.
J. R. Wright and T. J. Klingen, J. Inorg. Nuclear Chem., 1973, 35, 53.
J. B. Moffat, J. Mol. Structure, 1973, 16, 307.

140
(vl 3675 cm-l, v2 2035 cn1-l for llB, 14N),while borazine gave rise to products
in which ring-opening, loss of H, and formation of multiple BN bonds
occurred.140
Microwave spectra assignable to gas-phase aminodifluoroborane BF,(NH,)
have been detected in the reaction mixture BF,
NH,. From an analysis of
data derived from 11BF,14NH2, 1BF214NH,, 11BF,15NH,,10BF,15NH,,
l1BF,l4ND,, and 10BF,14ND2it was concluded that the molecule was planar
(52), with r(BF) 1.33, r(NH) 1.00, r(BN) 1.40w; LFBF 118', LHNH 117',
and p = 2.595(30) D.141 The B-N distance is very similar to that found in
borazine (1.44 A), in agreement with the double-bond character which must
be postulated from the planar geometry.
The gas-phase reaction between BCl, and NH3 gives rise to C12BNH2,
which can be condensed out at -100 O C . It was characterized by mass and
i.r. spectra.14,
MO calculations on bis(amino)diborane(4) H&-BH-BH-NH,
and
(amino)vinylborane H,C=CH-BH-NH,
have been used to rationalize
differences in the photochemical reactivity of >C==C-C==c(
and
>N--B-B-N<
systems.I43
Tris-(2,2-dimethylhydrazino)borane B(NHNMe,), crystallizes in the
hexagonal system, with the space group P63/m (a = 8.187 f 0.004, c =
10.375 f 0.006A).144 The BN, skeleton is planar, with the methyl groups
symmetrically above and below this plane, giving a molecular symmetry of
Csh.The B-N bond distance is 1.420 f 0.014 A.
(Diphenylmethy1eneamino)dimesitylborane (MqH,C,),BN=CPh,
forms
orthorhombic crystals (space group Pbca, a = 17.36, b = 29.25, c = 10.12
A; 2 = 8). The >BeN=C< system has an allene-like geometry, with
r(B*N) 1.38(2), r(C=N) 1.29(2) A; LBNC 173(2)'; and a mean value of
r(BC) 1.59(2) A. M O calculations suggest bond orders of 1.6 ( B e N ) and
1.8 (C=N).145
Treatment of K+[Me,NBH,]- in diglyme with a three-fold excess of
NaBH, gives a solution of Na+[Me,N(BH,),]-, which may be converted into
p-Me,NB2H5 by addition of half-molar proportions of iodine. This is the
140
141
143
143
144
146
E. R. Lory and R. F. Porter, J. Amer. Chem. SOC.,1973, 95, 1766.

F. J. Lovas and D. R. Johnson, J. Chem. Phys., 1973,59,2341.
C. T. Kwan and A . A. McGee jun., Inorg. Chem., 1973, 12, 696.
A. K. Uriarte and K. G. Hancock, Inorg. Chem., 1973, 12, 1428.
H.Noth, R. Ullmann, and H. Vahrenkamp, Chem. Ber., 1973, 106, 1165.
C. J. Bullen, J.C.S. Dalton, 1973, 858.
141
first recorded preparation of this compound which does not involve the use of
B2H6.146
A microwave study of 7 isotopic species of Me2NB2H5leads to the molecular parameters listed in Table 1?47
Table 1 Molecular parameters for Me2NB,H,
1.916 f 0.004
1.191 f 0.010
0.003
1.365 f 0.006
1.544 f 0.010
1.488 f 0.010
119.6 f 0.5
89.1 f 0.9
76.8 f 1
110.0 f 1
16.7 f 1
E is the angle made iy the BH, plane and the plane perpendicular to tAle C,, symmetry
axis.
The displacement of B2H6 from B5H, has been observed to occur by the
action of strong bases (NH,, amines, or phosphines).14*The natures of the
final products suggested that a sequence of steps of the following type may be
postulated :
+
+
+
IzNH,
B5HB--t BH,
B4H6,nNH3+ resins
NH3
BH3 + H,N,BH, + H2
H2NBH2
HZNBH,
BH:, + HZNBZHb
201[zN,BHz),
6HzNW& --+ 3BzHs
3(HaNBHz), 4 3Ha
WNBH),
+ H2
Thus, strong bases are acting to liberate the strong Lewis acid B2H6, i.e.
bases strong enough for irreversible attachment to BH, can actually liberate
it by action on B,H,.
It has been shown to be possible to carry out the conversion:
with no loss of H2 by performing the reaction in a polyether solvent in the

presence of small amounts of
All 20 of the possible boron trihalide adducts of NMe, have been detected
(halogen exchange to give the mixed halide species only occurs when an
excess of BX, is present).150 In contrast to the free boron trihalides and their
O-donor adducts, the N-donor adducts allow isolation of the individual
146
14'
14'
149
lSo
P. C. Keller, Synth. Inorg. Metal-org. Chem., 1973, 3, 307.

E. A. Cohen and R. G . Beaudet, Inorg. Chem., 1973, 12, 1570.
A. B. Burg, Inorg. Chern., 1973, 12, 1448.
E. Mayer, Inorg. Chern., 1973, 12, 1954.
B. Benton-Jones, M. E. A. Davidson, J. S. Hartman, J. J. Klassen, and J. M. Miller,
J.C.S. Dalton, 1972, 2603.
142

mixed-halogen species, because of the slow halogen redistribution. l H chemical shifts were reported for all of the adducts, being within the range defined
by BF3 (2.60 p.p.m. downfield of TMS) and BI, (3.35).
Displacement reactions of trimethylamine-fluoroboranesMqN,BH&,F,
(n = 0-3) indicate that BF3 is a stronger Lewis acid towards NMe, than
BH2F, BHF,, or B2H6. The relative acidities of the last three compounds
could not be determined, however.151
Amine-boranes have been shown to react cleanly with halogenocarbons to
give amine-halogenoboranes and an alkane.152
The ground-state rotational spectra of 10 isotopic species of trimethylamine-borane [M%N10BH3, Me,Nl1BH3, Me,Nl0BD,, M%N11BD3, Me,Nl1BD,H, (CD3),NloBH3, (CD,),N1lBH3, (CD3),Nl0BD3, (CD3),Nl1BD,,
and (13CH,)(12CH3)2N11BH3]have been ana1y~ed.l~~
The following structural
parameters were obtained: r(BH) 1.211 f 0.003, r(NC) 1.495, r(BN)
1.609 A; LNBH 105.32 f 0.16", LBNC 110.9'. The dipole moment is
4.59 f 0.13 D , and a lower limit to the barrier to internal rotation of the
BH, group was estimated at 3.4 kcal mol-l.
Molar Kerr constants have been reported154for BH, and BX, (X = all
halogens) adducts of NMe, in dioxan and benzene solutions. The anisotropic electron polarizabilities of the adduct molecules were derived from the
measurements in dioxan solution and these were found to indicate an overall
reduction in polarizability on adduct formation.
CND0/2 calculations have been carried out on X,N,BY, (where X, Y = F
and H) with the aim of determining their optimum geometries.155 Fluorination was shown156to have a significant effect on the geometrical and electronic properties of these molecules.
Similar calculations were reported15' for Me,N,BMe,, Me,N,BCI,, Me,N,AlMe,, Me,N,AIH,, and Me,N,AICl,. These showed that the amount of
charge transferred from donor to acceptor increases as the substituents on
the acceptor become more electronegative. The resulting net negative charge
on the acceptor is carried by the substituents, and the resulting net positive
charge on the donor by the methyl groups. The calculations suggested that,
with the possible exception of Me,N,BCI,, a staggered conformation would
be predicted (as is found experimentally for the A1 complexes).
The electrolysis of sodium tetrahydroborate in ethylenediamine produces
the adduct ethylamine-borane, EtNH,,BH3.l5*This formulation, rather than
as the aminoborane EtNHBH,, was suggested by the vibrational spectrum,
lS1
J. M. VanPaaschen and R. A. Geanangel, lnorg. Nuclear Chem. Letters, 1972,8,879.
152
G . E. Ryschkewitsch and V. R. Miller, J. Amer. Chem. SOC.,

1973,95, 2836.
J. R. Durig, Y. S. Li, and J. D. Odom, J. Mol. Structure, 1973, 16, 443.
R. S. Armstrong, G. J. Peacock, K. R. Skamp, and R. J. W. Le Fevre, J.C.S. Dalton,
1973, 1132.
M.-C. Bach, J. Chirn. phys., 1972, 69, 1775.
M.-C. Bach, F. Crasnier, J.-F. Labarre, and C. Leibovici, J. Mol. Structure, 1973, 16,
89.
0. Gropen and A. Haaland, Acta Chem. Scand., 1973,27, 521.
L. A. Melcher, I. A. Boenig, and K. Niedenzu, Inorg. Chem., 1973, 12, 487.
lb3
155
156
lG7
158
143
especially the positions of the v(BH) and v(NH) modes. Thermal decomposition of ethylamine-borane gives tris(ethylamino)borane, B(NHEt)3.
CND0/2 calculations on (1,l -dimethylhydrazine)BF, are in agreement
with the experimental observation that the B is attached to the nitrogen atom
bearing the Me groups : [H,N-N(Me),.BF,].159
The changes which occur during the formation of donor-acceptor complexes between NH,, EtNH,, MeCN, pyridine, and 2,6-lutidine and BF, have
been investigated by X-ray photoelectron spectra and both ab initio and
semi-empirical MO calculations.160It was concluded that the change in
charge distribution on formation of the N-B bonds is reflected in the
change in the core ionization potential of both the N and B atoms. The calculated values for the extent of charge migration are found to be over-estimates, and the boron 1s ionization potentials reflect the degree of a-donation
to the B, and hence the strength of the B-N bond.
MO calculations have been performed on aziridine-borane (53).161 A very
minimal gaussian basis set was used, and the conclusion was drawn that the
B-N bond is very covalent, owing to substantial donation of the nitrogen

lone-pair in classical dative-bond fashion, and also owing to endocyclic
charge transfer from the endo-methyleneproton to the endo-borane proton.
A study has been made162of the dehydrohalogenation reactions of BI,aromatic amine adducts. The main difference between these and analogous
systems containing other boron halides is that formation of 1,3-diaza-2,4diboranaphthalene derivatives is more extensive for the BI, systems.
Reactions of dimethylaminodifluoroarsine Me,NAsF, with BF,, B,H,, and
BH,CO lead to co-ordination of BF3 at the N atom but BH, at the As
a tom.163
llB and 14N chemical-shift data have been tabulated for a series of
amino(a1koxy)-, amino(alky1thio)-, and 1-pyrr~lyl-boranes.l~~
Treatment of TiBr, with excess bis(dimethy1amino)bromoborane (Me,N),BBr yields the 2: 3 adduct [(Me,N),BBr],[TiBr,],.1s5 1.r. spectra were consistent with the formulation :
Br4Ti+--NMe2B(Br)Me2N--+TiBr4+NMe2B(Br)Me2N+TiBr4
M. Graffeuil, J.-F. Labarre, C. Leibovici, and E. Taillandier, J . Mol. Structure, 1973,
15, 367.
I8O M. Barber, J. A. Connor, M. F. Guest, I. H. Hillier, M. Schwarz, and M. Stacey,
J.C.S. Faraduy 11, 1973, 69, 551.
161 J. A. Kroll and D. D. Shillady, J. Amer. Chem. SOC.,1973, 95, 1422.
lea J. R. Blackborow and J. C. Lockhart, J.C.S. Dalton, 1973, 1303.
163 J. G. Morse and K. W. Morse, Inorg. Chem., 1973, 12, 2119.
184 H. Noth and B. Wrackmeyer, Chem. Ber., 1973,106, 1145.
166 M. R. Suliman and E. P. Schram, Inorg. Chem., 1973,12,920.
lSB
144
Compounds of the type R~P(S)-NR2-BR~ [R1 = Me, Ph, Me,N, or

CH,(Me)N; R2 = Me, Et, or Ph; R3 = Me or Et] are obtained by (a) Si-N
bond cleavage of R',P(S)-NR2-SiMe3, (b) the reaction of N-metallated
thiophosphoryl- or thiophosphinyl-amines with diorganoboron halides,
or (c) the addition of sulphur to RiP-NR2-BRi. N.m.r. studies on these
compounds indicated that the barrier to rotation about the B-N bond is decreased by introducing the R,P(S) group on the N atom of a monoaminoborane, implying a weakening of the B-N bond.166
SS-Dimethyl-N-(trimethylsily1)sulphoximide O=S(Me),=NSiMe, reacts
with BF, to give Me3SiF and substituted iminoboranes F,B
[N(O)SMe,],
(n = 1 or 3, but not 2).16' The compound with n = 1 is polymeric, but when
n = 3 it is a monomer.
N-Methyl(sily1amino)- and N-methyl (stanny1amino)-boranes are formed
in the reaction of N-lithioaminoboranes with methylsilyl or methylstannyl
chlorides, although yields are satisfactory only when the metallation of the
aminoboranes proceeds without side reactions.168
A number of new aminoboranes containing Si-N-B,
Ge-N-B,
or
Sn-N-B
linkages have been prepared.169Thus, addition of LiN(SiMe,),
to PhBCI, gave (Me,Si),NB(Ph)CI. The lithium salts of (Me3E),(But)2-nNH
(E = Si or Ge; n = 1 or 2) reacted with Me,N-B(Ph)CI, giving the bisThe tin compounds (Me@),aminoboranes (M%E),(But),,NB(Ph)NMe,.
NB(X)NMe, (X = Ph or NMe,) were prepared by the cleavage reaction of
(Me,Sn),N with chloroboranes Me,NB(X)CI.
The compounds (54) [L = C(O)CH=CHMe or CH=CHMe] have been
isolated from the reaction of (C,H,)Fe(CO),I with K[HB(C,H3N,)3].170
(54)
14N n.m.r. spectra have been reported for MeZMN3, where M

Al, or
Compounds containing B-P
or B-As
Bonds.-Microwave
= B,
spectra in the
P,K, and R bands of 16 isotopic species of phosphine-borane H,PBH, have

166
16'
16*
16Q
170
171
H. Noth, D. Renier, and W. Storch, Chem. Ber., 1973, 106, 1508.

F. Knole, M. L. Anagnostopulos, and R. Appel, Chem. Ber., 1973,106,2089.
1. Geisler and H. Noth, Chem. Ber., 1973, 106, 1943.
R. L. Wells and R. H. Neilson, Synth. Inorg. Metal-org. Chem., 1973, 3 , 137.
R. B. King and A. Bond, J. Organometallic Chem., 1972, 46, C53.
J. Miiller, J. Organometallic Chem., 1973, 51, 119.
Elements of Group XI1
145
been observed, and the following structural parameters were determined :
r(BH) 1.212 f 0.002, r(PH) 1.399 f 0.003, r(PB) 1.937 f 0.005 A; LBPH
116.9 f 2O, LPBH 103.6 f 0.2", LHPH 101.3 f 0.2O, and LHBH 114.6 f
0.2'. The molecule was in the staggered conformation, with a barrier to
internal rotation of 2.47 f 0.05 kcal mol-l, while the dipole moment,
obtained from the Stark splittings, was 4.00 f 0.03 D.172
CNDO MO calculations on H3PBH317, are in agreement with the above
observation that the staggered conformation is the most stable. The barrier
to rotation and dipole moment had calculated values of 2.72 kcal mol-l and
3.16 D, both in very reasonable agreement with experiment. In addition, an
ab initio calculation has been carried out on this molecule, using STO-3G
basis sets.174The inclusion of phosphorus d-orbitals appears to show that
they are significant. The barrier to internal rotation, calculated at the 'minimum energy' geometry, is ca. 1.2 kcal mol-l, but ca. 2 kcal mol-l at the
'experimenta1' geometry.
1.r. and Raman spectra of H,P,BCl, and D,P,BCI, at -196 OC have been
reported and assigned, on the basis of C,, symmetry.175 A normal-coordinate analysis was carried out, indicating a force constant of 1.96 mdyn
for the P-B stretch. Similar experiments and calculations on Me,P,BH,
and Me3P,BD317sshow that v(PB) and v(PC) are extensively mixed, while the
P-B stretching force constant in this case is 2.37 mdyn A-1.
Experimental dipole moments for a number of phosphine-boranes have
been measured:177 MePH2,BH3 4.58 D, Me2PH,BH, 4.78 D, and Me3P,BH,
4.97 D.
Sparingly soluble adducts are formed between PH, and boron trihalides,
and the mixed species H,P,BX,Y (X # Y = C1, Br, or I), H,P,BCIBrI, and
(probably) H3P,BBr2Fand H,P,BBrF, have been identified by lH n.m.r.17*
N.m.r. parameterswerealsoquotedforH,P,BX,, CD,PH,,BY,Z (Y # Z = F,
C1, Br, or I), and CD,PH,,BY,.
Base-displacement reactions and lJBp coupling constants have been
measured for a series of difluorophosphine-borane adducts RPF,,BH,.170
The former suggested the following series of base strengths: R = Me >
Me,N > Me0 > MeS, while the coupling constants decreased in the
series R = Me,N > Me0 > Me > MeS.
A number of difluorophosphites react with borane, and it has been
showdso that their base strengths in this reaction are in the sequence
17*
173
174
17&
176
177
17*
17Q
lSo
J. R. Durig, Y. S. Li, L. A. Carreira, and J. D. Odom, J . Amer. Chem. Soc., 1973,95,

249.
M.-C. Bach-Chevaldonnet, J.-F. Labarre, and C. Leibovici, J. Chim. phys., 1973, 70,
1181.
J. R. Sabin, Chem. Phys. Letters, 1973, 20, 212.
J. D. Odom, S. Riethmiller, J. D. Witt, and J. R. Durig, Inorg. Chem., 1973, 12, 1123.
J. D. Odom, B. A. Hudgens, and J. R. Durig, J. Phys. Chem., 1973,77, 1972.
J. G. Morse and R. W. Parry, J. Chem. Phys., 1972, 57, 5365.
J. E. Drake and B. Rapp, J.C.S. Dalton, 1972, 2341.
R. Foester and K. Cohn, Inorg. Chem., 1972, 11, 2590.
E. L. Lines and L. F. Centofanti, Znorg. Chem., 1973,12, 21 11.
146
PF2OEt > PF20Me > PF20CH2CF3.This basicity order is matched by the

series of lJBpcoupling constants in the adducts.
Ten adducts L-+BH,Cl,-,
(n = 0-3),
L-43HnBr,,
(n = 1-3),
L-+BCI,Br,,
(n = 1 or 2), and L+BHBrCl (L = PMe,) have been subjected to intensive n.m.r. study (lH, llB, and 31P).181 The only parameter
which correlated with the thermodynamic stability of these adducts was the
screening constant of the protons P-C_H,. This is consistent with the idea
that in studying the formation and behaviour of such complexes one must
consider the whole molecule and not just effects on the donor-acceptor bond
itself.
The previously unknown phosphine-bridged diborane B2PH, ( 5 5 ) has been
obtained in good yield by treating H,P(BH,);Naf
with dry HCl at low
temperatures.ls2 N.m.r. data exclude the alternative bis(b0rane)phosphine
(56) and 7-phosphino-borane (57) structures. CND0/2 calculations1s3for the

structures (55) and (56) agree with the experimental order of stabilities of
the two forms. Data were also presented to show that the CNDQ/2 method
is applicable for compounds containing B, P, and H atoms, by comparison
with ab initiu calculations, but that the former could indicate erroneous
charge distributions in the P-H bonds.
The crystal structure of bis(tripheny1phosphine)-diborane(4) B2H4,2PPh3
has been determined:ls4 the crystal is triclinic (space group Pi),with a =
9.119(2), b = 9.360(2), c = 11.201(2) A; a = 77.574(8)', #? = 109.831(8)0,
and y = 1 19.202(8)0.The central B2H4P2 skeleton has an ethane-like structure
in the anti-conformation (58). Detection of the H atoms by a difference
Fourier synthesis clearly eliminated a bridging structure. The following bond
lengths were reported: r(BB) 1.76(2), r(BH) (average) 1.20(3), and r(BP)
1.935(9) A.
(58)
lS3
18*
(59)
J.-P. Laussac, G. Jugie, J.-P. Laurent, and F. Gallais, Compt. rend., 1973, 276, C,
1497.
H. Hofstotter and E. Mayer, Angew. Chem. Internat. Edn., 1973, 12, 413.
B. M. Rode and H. Hofstotter, Monatsh., 1973, 104, 1090.
W. Van Doorne, A. W. Cordes, and G. W. Hunt, Znorg. Chem., 1973, 12, 1686.
147
CND0/2 calculations on the electronic structure of MeH,P,BH3 indicate

that the most stable conformation is (59), in agreement with microwave
results.ls5Barriers to internal rotation about the P-C and P-B bonds were
calculated to be 3.3, 3.4 kcal mol-l, respectively.
Molecular-beam mass spectrometry was used to characterize (Me,N)FZP,11B3H7,(Me,N)F,P,lOB,H,, and F3P,B3H7,and their pyrolysis products.ls6
These data showed that the first two decomposed via B,H7, for which mass
spectra were presented for the first time. The low parent-ion intensity of
B3H: suggests that B3H, may be classified as an unstable borane. Roomtemperature decomposition of (Me,N)F,P,B,H, also gave (Me2N)F2P,B4Hs,
which in turn decomposed via B4Hs.
Sodium bis(borane)dimethylarsenide(l -) is prepared by the reaction :
NaAsMe,
+ B,H,
Na[Me,As(BH,),]
This compound was characterized by its llB n.m.r. spectrum and a number of
reactions.ls7
Boron Halides.-Timms has published a short review on the preparation

and properties of boron subhalides.lss
Resonance fluorescence has been observed from diatomic BF produced
in a microwave discharge.189
Ab initio SCF-MO calculations have been performed on BF,, and alterations in predictedgeometrieswith different gaussian-orbita1 basis sets noted .lgo
Further non-empirical SCF calculations on this molecule have been reported
by Rothenberg and Schaeffer.lgl Values of the dipole moment, quadrupole
moment, octupole moment, second and third moments of the electronic
charge distribution, diamagnetic susceptibility, and electric field gradient
were caIculated.
In conjunction with a study of bonding in the nitrate ion, Maria et al. have
reported the electronic absorption spectra of all four boron halides BX3.192
Vacuum-u.v. spectra of BF,, BCI,, and BBr, have been obtained, and
tentative assignments made.lg3 The lowest-frequency band in BCI, and
BBr, is assigned to a valence-shell transition of the T*+ T type.
Photoelectron spectra have been observed for BX, and BX2Y species
(where X, Y = F, C1, Br, I, NMe,, or Me).lg4These were assigned, for the
trihalides, on the basis of (i) line shapes, (ii) calculations of spin-orbit
F. Grasnier. J.-F. Labarre, and C . Leibovici, J. Mol. Structure, 1972, 14, 405.
R. T. Paine, G. Sodeck, and F. E. Stafford, Inorg. Chem., 1972,11, 2593.
L. D. Schwartz and P. C. Keller, Inorg. Chem., 1973, 12, 947.
lS8 P. L. Timms, Accounts Chem. Res., 1973, 6 , 118.
lS9M. B. Moeller and S. J. Silvers, Chem. Phys. Letters, 1973, 19, 78.
l g oC. Thomson and D. A. Brotchie, Chem. Phys. Letters, 1972, 16, 573.
lgl S. Rothenberg and H. F. Schaeffer tert., J . Amer. Chem, Soc., 1973, 95,2095.
l S 2H. J. Maria, J. R. McDonald, and S. P. McGlynn, J . Amer. Cnem. SOC.,
1973, 95,
1050.
Ig3 A. A. Planckaert, P. Sauvageau, and C. Sandorfy, Chem. Phys. Letters, 1973,20, 170.
lg4 G. H. King, S. S. Krishnaniwthy, M. F. Lappert, and J. B. Pedley, Furuduy Discuss
Chem. SOC.,1973, 54, 70.
lS5
lS6
11
148
coupling and of orbital energies as a function of distortion, and (iii) comparison with other BX,-type species. Assignments for the other compounds
were also proposed, but calculations for the more complex species did not
prove to be very informative.
CND0/2 MO calculations on BX, and BX; (where X = H, F, or C1)
reproduce the observed lengthening of bonds on going from three- to four-coordination, but the absolute values calculated were too large.lg5
Calculations on excited states of BF, using a gaussian basis set suggest that
the orbitals fall into two classes-one localized within the ring of fluorine
atoms and the other outside this ring.lg6
Ab inifio calculations on BF,, BF;, and B2F4gave calculated geometries
which were in good agreement with experimental values (especially the
fact that B-F distances are very similar in BF, and B,F,, but significantly
longer in BF;).lg7 Ionization potentials were calculated to be significantly
too low, and stretching force constants too high, however. A different ab
inifio calculation for BF,, and also BCI,, on the other hand, produced
calculated ionization potentials in good agreement with those obtained
experimentally from photoelectron spectra.lg8
CND0/2 and INDO calculations on BF,OH confirm the experimental
finding that the molecule is completely planar, and suggest a barrier to
rotation of the proton of 6.74 kcal mol-l (CND0/2) or 7.01 kcal mol-1
IND DO).^^^
Rate-constant measurements have been made200 on the reactions of
NH, + NMe, and NMe2H NMe, mixtures with BF,.
Displacement of the F- ion from BF; has been observed when M(BF&
(M = Co, Ni, or Cu) is refluxed with quinuclidine or triethylenediamine
(L) in a THF-dimethoxypropanol solution, producing F,BL.201
If solid boron nitride is subjected to U.V. irradiation in the presence of a
4: 1 mixture of F,
02,NO+ BF, is produced.202This is a much simpler
process than those involved in earlier synthetic routes to this compound.
Fluoroborate equilibria have been examined in 1 molar NaCl solution,
measuring [F-] with a LaF, electrode and the pH using a hydrogen electrode.
The results may be explained in terms of the following reactions and equilibrium quotients :
B(OH),
B(OH),
lg5
lg7
lg8
2oo
201
202
B(OH), 3- F2FH+
3F2H+
+
+
+
+
+ BF(0H)I;
+ BF,(OH), + H2O
+ BF,(OH)- + 2Ha0
log Q = -0.36 f 0.2

log Q = 7.06 f 0.02
log Q = 13.689 f 0.003
C. Leibovici, J. Mol. Structure, 1972, 14, 459.

B. Cachiolo, V. Pincelli, E. Tosatti, U. Fano, and J. L. Delimer, Chern. Phys. Letters
1972, 17, 15.
N. J. Fitzpatrick, Znorg. Nudear Chern. Letters, 1973, 9 , 965.
D. Goutier and L. A. Burnelle, Chem. Phys. Letters, 1973, 18, 460.
C. Leibovici and J.-F. Labarre, J. Chim. phys., 1972, 69, 1571.
S. Glicker, J. Phys. Chern., 1973, 77, 1093.
T. R. Musgrave and T. S. Lin, J . Co-ordination Chem., 1973, 2, 323.
J. L. Adcock and R. J. Lagow, J. Fluorine Chem., 1973,2,434.
149
the last being the major species formed. These, together with previously
known equilibrium quotients, give the following log Q values for the stepwise
displacement of OH- by F-, from B(OH)h to BF,: -5.3 f 0.2, -6.3 f 0.2,
-7.10 f 0.02, -8.40 f 0.1.203
lgF n.m.r. spectra have been measured for BF, solutions containing
BFy , BF,(OH)-, BF,(OH);, and BF(OH);.204 The following deductions were made: (a) approximate values for the equilibrium quotients
Q,,,,where Q,,,= [BF,(OH)3_,]/[B(OH),][F)"[H+ly,
and x = 1, 2, or 3,
y = 0,1, or 2, could be calculated; (b)the rates of fluorine exchange were in
the order BF, < BF3(OH)- < BF,(OH), < BF(0H);; and ( c ) the 19F
chemical shifts were in the same sequence.
A d.t.a. study of HN0,-BF, mixtures revealed the existence of a single
compound HNO3,2BF, (m.p. 420C).,05 This was confirmed by Raman
spectra of the liquid state which indicate the presence of the nitronium ion
NO:, i.e. the complex may be formulated as NO: [(BF,),OHr. The structure
of the anion was not discussed in this paper.
lH and 19Fn.m.r. spectral studies have been made on the mono- and
di-hydrates of BF,. Calculated bond lengths in the dihydrate are consistent
with the ionic form H30f[BF3(0H)]-, although the non-ionized form (60) is
not entirely excluded. The monohydrate is a simple donor-acceptor complex

H 2 0 -+BF3.206
1.r. and Raman spectra of LiBF,,nH,O and LiBF,,nD,O (n = 1 or 3),
were obtained over the temperature range -125 to +20 OC.,07 Assignments
to anion and crystal water bands were made, the latter being discussed in
terms of the strength of hydrogen-bonding interactions.
The temperature dependence of 19Fn.m.r. parameters of BF; in acetone
and H,O-acetone solutions has been discussed in terms of the different
possible F-exchange processes.208
Detailed n.m.r. measurements on the complex MesNBF, show209that the
sign of the B-F coupling constant is opposite to the signs of the B . - - H
and F - * H coupling constants.
203
204
2os
206
207
208
20*
R. E. Mesmer, K. M. Palen, and C. F. Baes jun., Inorg. Chern., 1973, 12, 89.
R. E. Mesmer and A. C. Rutenberg, Inorg. Chem., 1973,12,699.
R. Fourcade and G. Mascherpa, Bull. SOC.chim. France, 1972, 4493.
C. Gascard and G . Mascherpa, J . Chim. phys., 1973, 70, 1040.
M. Manewa and H. P. Fritz, 2.Naturforsch, 1972, 27b, 1127.
B. N. Chernyshov, V. A. Shcherbakov, and R. L. Davidovich, Spectroscopy Letters
1972, 5, 421.
V. V. Negrebetskii, V. S. Bogdanov, and A. V. Kessenikh, J. Struct. Chem., 1972, 13,
150
H e 1 photoelectron spectra have been measured for B2CI, and B2F4and

interpreted on the basis of ab initiu SCF-MO calculations.210
The Raman spectra of solid and gaseous B2F4 have been recorded, and the
normal vibrational modes of the molecule assigned. No evidence could be
found for the conversion of the planar (&) into the non-planar (Dza)form
on passing from the solid to the vapour, as had been reported previously.211
A gravimetric method has been used to study the kinetics of the reaction:
2B(s)
+ BCl,(g) + 3BCl(g)
between 700 and 900C.212The reaction is first-order, with an apparent

activation energy of 52 kcal mol-l. The heat of adsorption of BCI, on the B
surface was found to be 37 kcal mol-l, and hence the surface-reaction step is
the rate-limiting stage in the process.
The rate constant of the red afterglow which arises from the reaction of
atomic hydrogen, H(2S), with BCI, is k = 46 s-l. An inverse predissociation
mechanism is believed to be responsible,213with a probable fast stage of
reaction being:
H
+ BCl,
BCl2'
+ HCl
Vibrational relaxation processes in llBCI, and 1BCI, have been studied by

i.r. double-resonance techniques.214
Interaction of quartz with BCl, or BBr, occurs above ca. 350 'C; with BCI,
a film of B,O, is formed, which passivates the quartz surface; a similar
reaction occurs with BBr,, but there is also thermal dissociation of the BBr,
itself, giving elementary B.215
The heats of solution of M+BCI; (M = K, Rb, or Cs) in aqueous alkali
have been measured, and their enthalpies of formation calculated, as follows:
(K+) -219.9 f 0.4, (Rb+) -222.8 f 0.5, (Cs+) -225.3 f 0.5 kcal mol-l.
The enthalpy of formation (AH;) of BCI; (g) calculated from these results is
-222 kcal mol-1.216
If NH4Cl is treated with either a mixture of BCI, and PCI, or with [PCI,]+
[BCIJa number of chlorophosphazonium tetrachloroborates [GI (CI,P=N),PCI,]+ [BCI,]- are produced.217The value of n depends chiefly upon the reaction temperature, and an excess of BCI,, gives no noticeable effect on the
course of the reaction.
210
211
212
*13
214
215
216
217
N. Lynaugh, D. R. Lloyd, M. F. Guest, M. B. Hall, and I. H. Hillier, J.C.S. Faraduy

II, 1972, 68, 2192.
J. R. Durig, J. W. Thompson, J. D. Witt, and J. D. Odom, J. Chem. Phys., 1973, 58,
5339.
V. A. Krenev and V. I. Evdokimov, Russ. J. Inorg. Chem., 1972, 17, 171.
B. Vidal, 0. Dessaux, and P. Goudand, J. Chim. phys., 1972, 69, 1586.
P. L. Houston, A. V. Nowak, and J. I. Steinfeld, J . Chem. Phys., 1973, 58, 3373.
B. A. Saveliev, V. A. Krenev, and V. I. Evdokimov, Izvest. Akad. Nauk. S.S.S.R.,
Neorg. Materialy, 1973, 9 , 325.
N. V. Krivtsov, K. B. Titova, and V. Ya. Rosolovskii, Russ. J. Inorg. Chem., 1973,18,
182.
K. Niedenzu, I. A. Boenig, and E. B. Bradley, 2. anorg. Chem., 1972, 393, 88.
Elements of Group IIZ

151
Normal-co-ordinate analyses have been performed on BC1,Br and BClBr,
which give good agreement between calculated and experimental wavenumbers.218
The i.r. spectra of OBCl and OBBr in argon matrices have been obtained,
and assigned as follows219(using C,, symmetry): 011B35Cl: v1 673, v2 4M,
v3 1958 cm'l; OllBBr; v1 535, v2 374, v3 1936 cm-l. OBI could not be
prepared.
A number of bands due to BBr may be detected220in a BBr3-He mixture
subjected to a discharge. They belonged to the a311to - X I P systems of
BBr, and could be analysed to give rotational constants for the a(1) and
a(O+)states.
A transient BI species has been detected221from the flash photolysis of BI,,
and its U.V. absorption spectrum (consisting of a band in the region 265-279
nm) has been measured. This could be analysed as the (1, 0 ) , (0, 0 ) , and
(0, 1) bands of the Al II+ XIC+ system, together with associated bands such
as (2,1), (l,l), and (1, 2) from vibrationally excited electronic ground-state
molecules. A tentative suggestion was made that the vibrational frequency of
this molecule might be ca. 800 cm-l.
Halogen exchange has been demonstrated222in the systems Me,TeCl,-BBr,
and TeCl,-BBr,. A very tentative suggestion was made that bridging intermediates might be involved.
A kinetic study of the halogen-exchange reactions :
RY + BXs 4 R X
BXaY
(where R = Prn, PI!, Bun, Bus, or MqSi; Y = C1 or Br; X = Br or I,

with X heavier than Y) indicates that the most likely mechanism for the
reaction involves initial formation of an adduct RY,BX,.223
Compounds containing B-0 Bonds.-The laser-excited fluorescence spectrum
of the short-lived species B02 has been observed and measured.224Analysis
of the spectrum yielded values of the vibrational constants in the electronic
ground state.
An anharmonic vibrational force-field has been calculated for the metaborate ion BO;, isolated in KCl and KBr l a t t i ~ e s . 2 ~ ~
MO calculations using the TDOA (Two-atom Differential Overlap Approximation) method have been reported for the isoelectronic series BOi-,
COi-,andNO;.22s
A. Muller, N. Mohan, P. Christophliemk, I. Tossidis, and M. Drager, Specfrochim.
a20
221
222
224
Acta, 1973, 29A, 1345.

A. Snelson, High Temperature Sci.,1972, 4, 318.
J. Lebreton, J. Chim. phys., 1973, 70, 738.
A. G. Briggs and R. Piercy, Spectrochim. Acta, 1973, 29A, 851.
M. T. Chen and J. W. George, J . Inorg. Nuclear Chem., 1972,34, 3261.
M. Goldstein, L. I. B. Haines, and J. A. G. Hemmings, J.C.S. Dalton, 1972, 2260.
D. K. Russell, M. Kroll, D. A. DOWS,
and R. Beaudet, Chem. Phys. Letters, 1973,20,
153.
a25
a26
D. F. Smith jun., J. Chem. Phys., 1973,58,4776.

S. P. Dolin and M. E. Dyatkina, J. Strucf. Chem., 1972, 13,906.

152
A detailed assignment has been
for the i.r. spectra (in the
1800-3600 cm-l region) of B(OH),, HB02, and B203.
Borane (BH,) reacts with methanol and propan-2-01 to give ROH,BH,,
ROBH,, (RO),BH, and H2.228The formation of the simple adduct precedes
further reaction. The estimated bimolecular rate constant for the BH3
Me,CHOH reaction is ca. lo8 mol-k1.
A reinvestigation of the Lewis acidity of trialkoxyboranes B(OR), shows
that, contrary to earlier reports, they do not form Lewis acid-base adducts
with N-bases. Onium salts of the tetra-alkoxyborate anion are formed
instead, for which the thermodynamic stability is critically dependent upon
the crystal lattice energy and temperat~re.~~
B(OPh),, on the other hand,
forms both an adduct and a piperidinium salt with piperidine.
A listing of thermodynamic data for a number of substituted triaryloxyboranes (XC,H,O),B, where X = nz- orp-C1, -Me, -OMe, or -CN, has been
made.230Similar data are reported for several quaternary ammonium salts of
the tetramethoxyborate anion,231e.g. AH&, = -1310.91 f 1.72 kJ rno1-l
for the piperidinium, -1266.5 f 1.5 kJ mol-l for the 2-aminoethylarnmonium salts, and -2486.0 f 2.0 kJ mol-l for ethylenediarnmonium ditetramethoxyborate.
A CND0/2 calculation of the conformation and electronic structure of the
molecule H,PO,BF, shows that formation of the donor-acceptor complex
leads to significant alterations in the effective charge at all of the atoms in the
molecule.232
MO calculations (also using the CND0/2 model) and a Mulliken population
analysis performed on the BF,,O=C(H)Ph adduct clearly favour a 0-0
bonding model, rather than one involving a charge-transfer interaction.233
lH n.m.r. data are consistent with 0

dialkylurea-BF, adducts (61).234
2a7
lZ8
229
230
231
232
233
234
--f
B co-ordination in a number of
P. Broadhead and G. A. Newman, Spectrochim. Acta, 1972, 28A, 1915.

T. P. Fehlner, Inorg. Chem., 1973, 12, 98.
J. W. Wilson, J.C.S. Dalton, 1973, 1628.
J. W. Wilson and J. T. F. Fenwick, J . Chem. Thrrmodynamics, 1973, 5 , 341.
J. W. Wilson, J.C.S. Dalton, 1973, 1631.
J.-F. Labarre and C. Leibovici, J. Chim. phys., 1933, 70, 687.
E. A. Castro and 0. M. Sorarrain, Theor. Chim. Acta, 1973, 28, 209.
J. S. Hartman and G . J. Schrobilgen, Canad. J . Chem., 1973, 51, 99.
153
1 :1 BF, adducts of glycine, a- and #?-alanine,and phenylalanine have been

synthesized.235Their i.r. spectra give evidence for the boron being coordinated to the oxygen atom of a carboxy-group on the amino-acid ligand.
BCl, reacts with pentafluoro-orthotelluric acid to give boron tris(pentafluoro-ort hotellurate) :
BCl,
+ 3HOTeF6 -+
3HC1
+ B(OTeF,),
This new compound was characterized by mass, n.m.r. (lgF),and i.r. spectroscopy. Unlike other boron compounds containing p-F atoms, it is thermally
stable up to 140 O C [when BF, and (OTeF,), are produced]. The acid strength
of B(OTeF,), is comparable with that of BCl,, possibly because competition
between B and TeF, for oxygen p-electrons leads to relatively little B t- 0
back-donation occurring.236
The crystal structure of the boron triethanolamine complex B(OC2H4),N
shows2,' that the boron atom is surrounded tetrahedrally, by 3 oxygen atoms
(B-0 1.431, 1.432, and 1.475 A) and the nitrogen atom (B-N 1.693 A),
Figure 12. There are no hydrogen bonds between the various molecules.
1.1571141
d)-8-&) 114.8
1 @"-B-N
1
L
drl- N - 8
a)N- B
dsl- N - 5
1017
104.5
m.0
703.9
1t i 1
7C89
a,,
Figure 12 Bond lengthslA and angles/' in B(OC,H,),N

(Reproduced by permission from Monatsh., 1973, 104,477)
235
236
937
M. Nakatani, Y. Takahashi, A. Ouchi, and K. Watanuki, Sci. Pap. Coil. Gen. Educ.
Univ. Tokyo, 1972, 22, 37.
F. Sladky, H. Kropshofer, and 0. Leitzke, J.C.S. Chem. Comm., 1973, 134.
H. Follner, Monatsh., 1973, 104, 477.
154

The heats of hydrolysis of MB(CIO,), (M = Rb or Cs) in 0.558 % NaOH
solution have been
and used to calculate AH; for [MB(C104)4
(cryst.)] at 298.15 K. The values obtained were -188.4 f 1.3 kcal mol-l
(M = Cs), -184.9 f 1.3 kcalmol-l (M = Rb).
Measurements of llB chemical shifts in sodium and potassium 1:1 borate
aqueous solutions may be used to obtain values for the equilibrium quotient
of the reaction :
which is 1.7 mol kg-l at 25 0C.239

A potentiometric study of complexes formed by boric acid or potassium
borate with mannitol in water or aqueous KCl solution has been carried
The formation constant K c l l of the mono-mannitoboric complex was
determined (pK,11 = 0.20 in H20 as solvent).
Raman spectra of aqueous solutions of borate anion in the presence of
ethylene glycol and mannitol have been reported.241They are consistent with
the formation of 1:1 and 2: 1 polyol: borate complexes. It was suggested that
the 2: 1 complex had C,symmetry, i.e. the five-membered ring is non-planar.
Spectroscopic (ix., u.v.-visible, and l H n.m.r.) data were given for a
number of boronium chelate salts of the type [BL,]+X-, where L, is ethyl
acetoacetate, 2-acetylphenol, etc., and X = SbCI;, ClO,, or
Factors influencingelectron delocalization in the chelate ring were considered
in detail.
The crystal structure of potassium boromalate KBC,H,O,,,H,O has been
determined.243The space group is P2, with 2 = 2 and a = 5.54(2), b =
11.98(2), c = 10.74(2) A; B = 113.2(5)'. The B atoms are tetrahedrally
co-ordinated to two malate ions via two oxygen atoms of each. The tetrahedron is distorted as shown in (62).
Refractive indices, densities, and relative viscosities have been reported for
a number of RbCI-H,BO,-H,O mixtures at 25 0C.244
238
239
240
241
242
243
244
N. V. Krivtsov, V. P. Babaeva, and V. Ya. Rosolovskii, Huss. J. Inorg. Chem., 1973,

18, 185.
A. K. Covington and K. E. Newman, J. Inorg. Nuclear Chem., 1973, 35, 3257.
L. ASSO,M. Asso, and G . Carponi, Rev. Chim. minirale, 1972, 9, 647.
J. Knoeck, J. Inorg. Nuclear Chem., 1973, 35, 823.
E. Ivfari and A. BarabAs, Rev. Roumaine Cfzim., 1973, 18, 667.
R. A. Mariezcurrena and S . E. Rasmussen, Actu Cryst., 1973, B29, 1035.
G. K. Gode and L. A. Klyavinya, Russ. J. Inorg. Chem., 1972, 17, 1495.

155
A study of the acidity constant of boric acid in synthetic sea-water (salinity
range 20-40%, ;temperature 5-30 "C)has been made, using potentiometric
tit ration^.^^^
Solubility isotherms for the LiB02-CO(NH2),-H20 system at 25 "C and
40 "C have been measured.246
A study of the PbF2-B203system247suggests that the reaction :
3PbFz
+ B20, -+
3Pb0
+ 2BF(gas)
has the greatest influence on the final phase composition.

The modifications induced in gelatinous silica by treatment with B203have
been
The nature of boron co-ordination in borosilicate glass may be investigated
by llB n.m.r. spectros~opy.2~~
When the Na20:B203ratio is 0.5 there are no
non-bridging oxygens, and the fraction of four-co-ordinate boron atoms is
equal to the Na20:B203ratio. When this ratio exceeds 0.5 the fraction of
non-bridging oxygens increases, as does the proportion of four-co-ordinate
boron.
A concentration cell of the type:
(Pt)O, I ZrO,(CaO) I Na,O-B,O,
(I) I I Na,O-B,O,
(11) I ZrO,(CaO) I Oz(Pt)
was used250to measure the thermodynamic activity of Na20-B,03 meIts.

Phase diagrams have been reported for the pseudo-binary systems
[K20,B20, (equimolar K20,6TiO2-K20,2B,O3)]and [Na20,B,03 (equimolar Na20,6Ti02-Na20,2B,03)].251
The miscibility gap in the system PbO-B203 has been examined in detail,
and a structural model devised to explain the observed b e h a ~ i o u r . ~ ~ ~
Gas-phase electron-diffraction methods have been
to study the
structures of the Group I (Li-Rb) metaborates MIBO,, at temperatures
between 1200 and 1550 K. The BOz group is linear in all cases, while the
MI-0 distance varies from 2.14 A for Na to 2.54 A for Rb.
The 3 crystalline forms of LiBO, have all been isolated under atmospheric
pressure, and the monoclinic form has been characterized. Li,B40, may be
prepared by a eutectic reaction at 545 "C in the Li20-B203 system; X-ray
powder-diffraction data were obtained for this species.254
246
246
247
248
240
250
251
253
253
254
I. Hansson, Acta Chem. Scand., 1973, 27, 924.

V. G. Skvortsov, Russ. J. Inorg. Chem., 1973, 18, 127.
Yu. L. Sapozhnikov, N. S. Andrushchenko, E. A. Bezrukova, A. G. Titova, and
B. T. Melekh, Russ. J . Inorg. Chem., 1972, 17, 444.
W. Heyer and F. Wolf, 2.anorg. Chem., 1972, 393, 50.
M. E. Millberg, J. G . O'Keefe, R. A. Kerhelst, and H. 0. Hooper, Phys. and Chem.
Glasses, 1972, 13, 79.
S. Sato, T. Yokokawa, H. Kita, and K. Niwa, J . Electrochem. SOC.,1972, 119, 1524.
A. J. Easteal and D. J. Edy, J. Inorg. Nuclear Chem., 1973, 35, 3041.
J. H. Simmon, J . Amer. Ceram. SOC.,1973, 56, 284.
Yu. S. Ezhov, S. M. Tolrnachev, and N. G. Rambidi, J. Sfrucf.Chem., 1972, 13, 910.
C. Maraine-Giroux, R. Bouaziz, and G. Perez, Rev. Chim. minkrule, 1972,9, 779.
156
MBO,, calcite-type, borates have been prepared255for M = Al, Gay and

TI, using high-pressure techniques. All were characterized by X-ray powder
diffraction, and indexed in the hexagonal system.
New mixed borates which are isomorphous with the mineral warwickite
(Fe, Mg), Ti(BO,), have been prepared, with the general formula M2+M3+
BO,, e.g. MgCrBO,, MgGaBO,, Mn11Fe111B04, CaInBO,,
Two borates with the olivine type ofstructure have been prepared by hydrothermal synthesis under high-pressure conditions : AlMgBO, (sinhalite) and
FeNiBO, (a new form of w a r w i ~ k i t e ) . ~ ~ ~
FeCoBO, also has the warwickite structure, containing a planar equilateral triangular BO, group, and octahedrally co-ordinated Fe and C o
atoms. The MO, octahedra share edges and form infinite bands four octahedra
Melting mixtures of NaF and B,O, at 800-900C gives NaF,B,O, and
NaF,2B20, as
They are glassy if the mixture is cooled immediately, but can be converted into crystalline forms by heating at 400-700 O C
for 40-200 h.
Potassium diborate crystallizes in the triclinic space group Pi (a = 6.484 f
0.002, b = 9.604 f 0.004, c = 10.413 f 0.005 A; 01 = 89.28 f 0.07",
/3 = 102.75 f 0.05', y = 101.25 f 0.05).260 The structure contains a
single three-dimensional borate ion framework, composed of mutually
linked planar BO, triangles, diborate, and triborate groups (in which two of
the three B atoms are tetrahedrally co-ordinated). Values of r(B0) for the
three-(1.369 A) and four-co-ordinate boron (1.477 A) are in the expected
regions.
Solubilitiesof Mg(OH),, Mg2B,0,,nH,0, MgB407,2.5H20, and Mg7B4013,7H2O in boric acid solution at 150 "C have been measured.261
The mineral johachidolite has been identified as CaA1B,O7, in which the
Ca is ten-co-ordinate (distorted pentagonal antiprism), the A1 is six-coordinate (octahedral), and the B is four-co-ordinate (tetrahedral).262The
structure is built up by the periodic tessellation of triangles, squares, and
hexagons, forming an MB307 lattice, with the Caz+ ions situated at the
centres of hexagons.
SO, reacts with Na,B,07 at 190-200 OC to give a mixed oxide B20,,2SO3
(boron disulphoxide) and a mixture of Na,B,(SO,), and Na2B20(S04)3.263
X-Ray data for the galloborate Li6Ga,(BO& show that the structure
256
256
257
z58
259
260
261
262
T. A. Bither and H. S . Young, J. Solid-state Chem., 1973, 6 , 502.

J. J. Capponi, J. Chenavas, and J. C. Joubert, J. Solid-state Chem., 1973, 7 , 49.
J. J. Capponi, J. Chenavas, and J. C. Joubert, Materials Res. Bulletin, 1973, 8, 275.
V. Venkatakrishnan and M. J. Buerger, 2. Krist., 1972, 135, 322.
V. M. Pavlikov, V. 0. Yurchenko, and I. E. Kir'yanova, Dopovidi Akad. Nauk.
Ukrain. R.S.R., Ser. B., 1973, 35, 540.
J. Krogh-Moe, Acta Cryst., 1972, B28, 3089.
P. P. Shamaev and A. P. Grigor'ev, Russ. J. Inorg. Chem., 1973, 18, 274.
P. B. Moore and T. Araki, Nature Phys. Sci., 1972, 240, 63.
S . N. Kondrat'ev and S. I. Melnikova, Russ. J . Inorg. Chem., 1972, 17, 1524.
157
contains infinite chains of the complex anion comprising two GaO, tetrahedra and two BO, triangles linked to each other by two further BO, triangles.
The lithium atoms are at centres of tetrahedra and form strips through the
structure. Sharing of oxygen atoms between Ga and Li tetrahedra also
occurs.264
X-Ray diffraction studies on single crystals of the following mixed borates
have been carried out :265*266 Pr2Sr3(B03),-orthorhombic, space group
P2,cn (CiJ, a = 16.45, b = 8.81, c = 7.38 A; Ga2Sr,(BO3),-isostructural,
a = 16.20, b = 8.62, c = 7.34A; and La2Ba,(B03)4-also orthorhombic,
but not isostructural with the first two. For the first compound, the presence
of triangular BOi- anions (B-0 distance 1.33 A) has been demonstrated,
with the Pr3+and Sr2+cations linking these into a three-dimensionalnetwork.
The following 3 compounds have been isolated from the Al(OH,)-B(OH),
system under hydrothermal conditions : A1,03,3B203,7H20-A1203,2B203,2.7H20, and 3A120,,2B20,. These decompose on heating to give
A120,,B20,.267
Measurement of solubility isotherms at 50 and 100 OC in the B203-PbOH 2 0 system enables the following solid phases to be identified: (at 50 "C)
Pb0,2B203,3H20; (at 100 "C) 4Pb0,5B2O3,2.5H2O,Pb0,2.5B203,2H20, and
3Pb0, 10B,0,,9H20.268
Examples have been given of calculations of the 'bond-valence' of B in a
number of borates, e.g. kernite [Na2B406(0H)2,3H20],gowerite [CaB,O,(OH)4,3H20],and K2B,08(OH),2H20.269
Accurate X-ray diffraction data have been used270to determine electron
densities in the mineral kernite [Na2B406(OH),,3H20].
The following compounds have been characterized in the B,O,-PbO-H,O
system at 75 "C: Pb0,2B,0,,3H20 - 4Pb0,5B20,,2.5H20, and 3Pb0,1OB,O,, 9H20.271
Sborgite [NaB50,(OH),,3H,0] crystallizes in the monoclinic space group
C2/c (a = 11.119, b = 16.474, c = 13.576A;
= 11250').272The pentaborate ion [B&(OH)4]- is made up of a double ring comprising one BO,
and four BO, units.
The compound Ca,B,O,Br crystallizes with orthorhombic symmetry
(space group Pnn2; a = 11.397, b = 11.255, c = 6.293 A). Chains of cornersharing BO, tetrahedra run in the z-direction. These are linked in the
24p
267
268
26n
270
271
273
G. K. Abdullaev and Kh. S. Mamedov, J. Struct. Chem., 1972,13, 881.

K. K. Palkina, V. G. Kuznetsov, B. F. Dzhurinskii, and L. G. Moruga, Russ. J. Inorg.
Chem., 1972,17, 341.
K. K. Palkina, V. G. Kuznetsov, and L. G. Moruga, J. Struct. Chem., 1972,13, 317.
H.-A. Lehrnann and K. Teske, Z . anorg. Chem., 1973,400, 169.
G. M. Smirnova, A. B. Zdanovskii, S. G. Sushkova, I. N. Zhitkova, 1. A. Leont'eva,
and Z. I. Sishkina, Russ. J. Inorg. Chem., 1973, 18, 271.
G. Donnay and J. D. H. Donnay, Acta Cryst., 1973, B29, 1417.
W. F. Cooper, F. K. Larsen, P. Coppens, and R. F. Giese, Amer. Mineralogist., 1973,
58, 21.
A. B. Zdanovskii, G. M. Smirnova, I. A. Leont'eva, and L. N. Kalitina, Russ. J. Inorg.
Chem., 1972, 17, 269.
S. Merlino and F. Sartori, Acta Cryst., 1972, B28, 3559.
158
x- and y-directions by boron atoms which occupy the centres of triangles of
oxygen atoms. The Ca2+and Br- ions are located in tunnels in the resulting
three-dimensional lattice.273
A number of complex intermediates have been detected and characterized
in the thermal decomposition of M0,3B203,10H20(M = Co or Ni), Mn0,3 H20.274
B2O3,3H20, and AI2O3,B2O3,
Single crystals of the lithium boracites Li4B7012Cl(with the Br and I
analogues) have been prepared275by the reaction of LiX LiB02,2H20
B203 H3B03(X = C1, Br, or I) in a sealed gold tube at 3 kbar and 700 'C.
X-Ray data on the C1 compound show that it belongs to the space group
F43c (T;), of rhombohedra1 symmetry.
The crystal structure of the boracite Mg,CIB,O,, consists of a boronoxygen framework which contains large interstices accommodating the
Mg2+and C1- ions. The asymmetric unit of the borate framework is shown in
(63). The same basic structure is found also in the iron-rich analogue
Fe*.aMgo.87013C1.276
The systems B,O,-MO-MZ (M = Mg, Mn, Fe, Ca, Zn, or Cd; Z = S ,

Se, or Te) give rise to two series of ternary compounds, boracites (M = Mg,
Mn, Fe, or Cd) or sodalites (M = Co or Zn).277
A number of borophosphates may be prepared278by heating together
-13P04and H3B03. Thus, at 3OO0C, BP04,3H20 is produced. Complex,
insoluble species are produced above 600 'C.
Compounds containing C-3
Bonds.-The B-C stretching vibration of
11BH3C0has been analysed to give values of B and D,, which are in agreement with those obtained from microwave spectra. Values of the rotational
constants B and D,, for the first-excited vibrational states of va and v4 v8
273
274
275
276
277
278
D. J. Lloyd, A. Levasseur, and F. Fouassier, J . Solid-State Chem., 1973, 6 , 179.

A. Dzene, E. Svares, and A. Ievins, Latv. P.S.R. Zinat. Akad. Vestis, Kim. Ser., 1972,
515, 544.
W. Jeitschko and T. A. Bither, Z . Naturforsch., 1972, 27b, 1422.
E. Dowty and J. R. Clark, Z . Krist., 1973, 138, 64.
A. Levasseur, B. Rouby, and C. Fouassier, Compt. rend., 1973, 277, C, 421.
S. I. Vol'fkovich, H. M. Al-Shenavi, L. V. Kubasova, and M. P. Zhuravleva, Zhur.
priklad. Khim., 1972, 45, 2137.
159
have been determined from the K = 0 sub-band of the main 'hot' band of
v4
vs - vg?79
The crystal and molecular structures of triborane(7)-carbonyl have been
determined.280The compound crystallizes in the space groupPl [a = 8.304(6),
b = 5.667(3), c = 5.683(3) A; a = 102.48(6)*, /?=75.96(7)', y =104.07(6)";
2 = 21, and the molecular structure is shown in Figure 13. The chief molecular parameters are: r ( C 0 ) l . l l ( l ) , r(CB) 1.54(1), r[B(l)B(2)] 1.89(1),
r[B(l)B(3)] 1.83(1), r[B(2)B(3)] 1.77(1) A, with r(BHterminal)lying in the
range 1.091-1.178 A, and r(BHbridge)being 1.354 A and 1.219 8, (i.e. the
hydrogen-bridge is unsymmetrical).
Figure 13 Molecular structure of triborane (7)-carbonyl

(Reproduced by permission from Inorg. Chem., 1973, 12, 2175)
Decomposition of I-B,H,, in pentane at -30 "C under 25 atm pressure of

CQ leads to the formation of B,H,,CO. Mass, lH and llB n.m.r., and i.r.
[v(CQ) 2160, v(BH) 2565 cm-l] spectral data were reported.2s1
The reaction of diborane in THF with HCN gives a product B,H,CN,THF,
which is best formulated as an internal salt in which the BHQ cation is
stabilized by co-ordination to the cyano-group of the cyanotrihydroborate
anion. This compound is unstable, but it can be converted into the more
stable pyridine and NMe, analogues. 1.r. and n.m.r. data confirm the formulation of these as D
279
280
2s1
282
--t
BH, +- N =C-BH,.2s2
L. Lambert, C. PCpin, and A. Cabana, J. Mol. Spectroscopy, 1972,44, 578.

J. D. Glore, J. W. Rathke, and R. Schaeffer, Znorg. Chem., 1973, 12, 2175.
R. Schaeffer and E. Walter, Itzorg. Chem., 1973, 12, 2209.
E. A. Lavrent'eva, G. V. Lagodzinskaya, M. L. Khidekel', 0. P. Shitov, L. Ioffe,
V. V. Negrebetskii, and V. A. Tartakovskii, J. Gen. Chem. (U.S.S.R.), 1973.43,294.
160
CNDO/S calculations on BMe,, BMe,(CH=CH,), BMe(CH=CH,),,

B(CH=CH,), , B-trimethylborazine, N-trimethylborazine, Me(CH,=CH)BCI, (CH,=CH),BCl, and ( C H 4 H ) B C l 2 give values for the energies of
singlet-singlet transitions in reasonable agreement with experiment.283
Lithium triethylborohydride LiEt,BH possesses enormous nucleophilic
power (lo4 times that of LiBH,).284
Controlled pyrolysis of a BBr,-CH,-H,
mixture over a BN surface at
1550-1650 O C produces a rhombohedra1 boron carbide B&2.285 This is
believed to contain icosahedral B,, units and linear CBC chains.
The reaction of borane with keten forms a single addition product BC,H,O
(bimolecular rate constant of formation = 4 x lo9 1 mol-l s-l at low partial
pressures of reactants).286Kinetic and mass-spectrometric data are consistent
with the formulation (64).
BH3
HaC=C=O
(64)
KGeH, and BMe, react to give KGeH,,BMe,.287 Hydrolysis of this product

gave H,, GeH,, and Ge2H, in varying amounts. The germane is produced by
attack on a GeH,BMe; ion thus:
GeH,BMe,
+ HzO + GeH, + MOBMe,
The H2and digermane were taken as evidence for an initial disproportionation

also taking place:
2GeH,BMe, + HBMe;
+ Ge,H,BMe;
These ions are then hydrolysed in a similar fashion to GeH,BMe;.
Boron-containing Heterocycles.-Ab initio MO calculations on the hypothetical 1,3,2,3-diazadiboretidine(65), the B-N analogue of cyclobutadiene,
H
R-N
../
I 1
,N-B
suggest288that by contrast with the latter a square geometry (here of D2,

symmetry) may well be preferred in this case.
G. Kuehnlenz and H. H. Jaffi, J. Chem. Phys., 1973,58,2238.
H. C . Brown and S. Krishnamurthy, J. Amer. Clzem. SOC.,1973, 95, 1669.
2 8 5 K. Ploog, J. Less-Common Metals, 1973, 31, 117.
T. P. Fehlner, J. Phys. Chem., 1972, 7 6 , 3532.
m7 E. R. De Staricco, C. Riddle, and W. L. Jolly, J. Znorg. Nuclear Chem., 1973, 35, 297.
288 N. C. Baird, Znorg. Chern., 1973, 12,473.
283
161
LCAO-MO-SCF calculations have been carried out for a number of

covalent B-N polymers.289 These include (HB=NH), , (BH2-NH2)n,
and the B- and N-chloro-analogues. Calculated bond structures were compared with results for the isoelectronic carbon systems.
An MO calculation has also been reported for borazine (as well as ethylene
and benzene), using the CNDO/2 approximation, and considering only the
conjugated r-electron system of the molecule.290Calculated values of the
first and second ionization potentials were in good agreement with experiment, and apparently reasonable values were obtained for the CT r charges.
Semi-empirical (Mulliken, Wolfsberg-Helmholtz) MO calculations on
halogenoborazines lead to the following conclusions :291 (a) the total
electron population of the ring decreases with halogen substitution at B
(the effects being greater for F than for Cl), (b) B-halogen substitution has a
greater effect on the charge of the ring than N-halogen substitution, (c)
the B-halogen and hexahalogen derivativeshave approximatelyequal r-electron
populations in the ring, and these are greater than those for the N-halogen
derivatives and borazine itself, which are themselves very similar, and ( d )
B-halogen substitution gives increased energy separation between bonding
and antibonding orbitals, thus stabilizing the borazine system more than
N-substitution.
The hydrolysis of 25 borazine derivatives in dilute 90% THF-10%H20
solutions follow pseudo-first-order kinetics.292The hydrolysis rates were
determined using a new analytical procedure, KBr0,-KBr solutions being
used to brominate the arylamine liberated. In N-phenylborazines, orthosubstitution in the phenyl ring decreases the rate of hydrolysis markedly.
Positional isomers have been isolated (using gas-chromatographic separation) and characterized when a number of 1,3,5-substituted borazines
were allowed to react with methyl or ethyl Grignard reagents as shown in
Scheme 1.293
Cy = cyclohexyl, R2 = Me or Et
Reagents: i, R2MgX-Et20
Scheme 1
2D0
2D1
2D2
893
D. R. Armstrong, B. J. McAloon, and P. G. Perkins, J.C.S. Faraday 11, 1973,69,968.

J. Gayoso, B. Maouche, and A. Boucekkine, Compt. rend., 1973, 276, C,257.
V. M.Scherr and D. T. Haworth, J . Inorg. Nuclear Chem., 1973, 35, 660.
I. B. Atkinson, D. C. Blundell, and D. B. Clapp, J . Inorg. Nuclear Chem., 1972, 34,
3037.
P. Powell, Inorg. Chem., 1973, 12, 913.
162
Inorganic Chemistry of the Main-group EZements
The thermal reaction of BCl, with o-toluidine gives the single trimer (66),
where Y = O - M ~ C ~ H , . ~ ~ ~
Y
clg/N\Bcl
YN\B"Y
c1
The mass spectra of a number of B-substituted derivatives of borazine and

N-trimethylborazine have been reported and a n a l y ~ e dB-Substituents
.~~~
are
more labile than the corresponding N-substituents, the six-membered-ring
fragments being stabilized by release of electron density from adjacent
N atoms. Borazines containing N-methyl substituents, however, lose a
hydrogen atom to form immonium-like fragment ions.
lH n.m.r. data have been tabulated for ten B-substituted N-trimethylborazines (67) in CCl,, C6H6, and C6D6 solutions, (R1= R2 = R3 = Me or
Me
C1 or Ph; R1 = R2 = Ph, R2 = Me or C1; R1 = R3 = C1, R2 = Me or Ph;

R1 = R3 = Me, R2 = Ph or Cl; R1 = Ph, R2 = Me, R3 =
The absorption spectrum of borazine vapour in the 2015-1800 8, region
consists of a single TP-T*, dipole-forbidden,electronictransition lA; c- lA'1.297
Faraday-effect studies on 26 D,, substituted borazines show that these
compounds possess a much greater magnetic rotation than corresponding
acyclic compounds.298This is analogous to the situation with aromatic hydrocarbons, and can be attributed to electron delocalization around the ring.
N-Trimethylborazine quenches the singlet state of benzene excited at 267
nm, but it does not affect the triplet state of benzene.299There is no evidence
for chemical reaction between N-trimethylborazine and benzene or biacetyl.
295
2g6
297
298
290
B. Frange, Bull. SOC.chim. France, 1973, 1216.

L. A. Melcher, J. L. Adcock, G. A. Anderson, and J. J. Lagowski, Inorg. Chem., 1973,
12, 601.
J. L. Adcock, L. A. Melcher, and J. J. Lagowski, Inorg. Chem., 1973, 12, 785.
E. R. Bernstein and J. P. Reilly, J . Chem. Phys., 1972, 57, 3960.
M. Pasdeloup and J.-P.Laurent, J. Chim. phys., 1973,70, 199.
C. D. Dejardins, F. Grein, M. E. Macbeath, J. Russmore and I. Unger, J . Photochem.,
1973, 1, 153.

163
N-trimethylborazine excited at 221 nm does not exhibit any fluorescence or
phosphorescence in either the gas phase or in a glassy matrix.
The Lewis basicity of the NMe, group in H,(NMe2)B3N3H,has been measured by using B,H, as a reference acid in competition reactions with other
bases. The following sequence for the NMe, Lewis basicity was proposed:
PhNMe,
>
H2(NMe2)B3N3H,> B(NMe,),
M;NC,H,N(Me) BtNMe,)
Thus the r-electrons of borazine are partially delocalized, and they have a
significantinfluence on the chemical properties of a ring s u b s t i t ~ e n t . ~ ~ ~
The observed line shapes for the lH n.m.r. spectra of borazine (as neat
liquid or as solute in perdeuterio-toluene,-DMSO, -chloroform, or -cyclohexane solutions) are dominated by broadening due to electric-quadrupoledependent nuclear spin-lattice relaxation of N and B. It appears that N and
B respond equally to rotational diffusion.301
The crystal structure of cycl~triborazane(BH~NH,)~,the
inorganic analogue
of cyclohexane, has been determined.302It belongs to the orthorhombic
space group Pbcm [a = 4.403(3), b = 12.210(7), c = 11.227(10) A]. The
molecule possesses a chair conformation, with symmetry close to C3v; the
molecular dimensions are shown in Figure 14.
H(le)
H( l a ) . .. . H ( 3 a ) = 2.74 A
H( 2 a ) .... H ( 4 a ) -2.67%,
H(2a)
Figure 14 Mo IecuIar dimensions1A and angles/" iiz (BH2NH2),

(Reproduced by permission from J. Amer. Chem. Soc., 1973, 95, 1480)
A simple synthesis, giving reasonable yields, has been developed for

cyclopentaborazane, (BH,NH,), :
H2B(NHJ2BH4
300
301
302
+ NH3
rnonoglyme
H,
+ H3BNH3 + ;(BH2NH2),
0. T. Beachley jun. and T. R. Durkin, Inorg. Chern., 1973, 12, 1128.

G. M. Whitesides, S . L. Regen, J. B. Lisle, and R. Mays, J . Phys. Chern., 1972, 76
2871.
P. W. R. Corfleld and S. G . Shore, J. Amer. Chern. SOC.,
1973, 95, 1480.
12

164
The desired product is insoluble in the solvent, and hence it may be isolated
very easily.303
BX, (X = F, C1, or Br) and AlCl, are transformed by MqSiN, in CH,C12
or ether into trimeric boron dihalide azide or into monomeric aluminium
dichloride azide (in CH,Cl,) or polymeric aluminium chloride d i a ~ i d e . 3 ~ ~
In the boron compounds, i.r. spectra are consistent with the presence of
bridging azido-groups, i.e. the structure is (68).
N
II
It
X2B/N\ B X2
I
(68)
1,1,3,3,5,5-Hexaphenylcyclotriborataphosphorinan (69) exists in two

crystal modifications (a,space group Pi,triclinic; /3, space group Zc or IZ/c,
r n o n o ~ l i n i c ) .The
~ ~ ~six-membered ring has the chair configuration, with a
/BH2
PhzP
'PPh2
I
I
I
H2B
\p/BH2
Phz
(69)
close approach to C,(rn) symmetry. The molecular dimensions provide no

evidence for B -+ P r-bonding; they are: r(BP) 1.948, r(BH) 1.11, r(PC)
1.823 A; LBPB 114.3", LPBP 112.6", LHBH 112', and LCPC 103.1'.
The first diazaborolin has been prepared, by the reaction shown in Scheme
2. Its identity was confirmed by lH n.m.r. data.306
Me
"TH2
- H2
Ph-B
____+
(Pd/C; 72 h)
NXHs
Me
Me
Ph-B
"I"
"43
Me
Scheme 2
Electron diffraction shows that (70) is essentially planar, but with a slight
deviation from planarity at the N at0ms.3~~
The most important bond lengths
303
304
305
306
307
E. Mayer, Inorg. Nuclear Chem. Letters, 1973, 9 , 343.

N. Wiberg, W.-C. Joo, and K. 13. Schmid, 2. anorg. Chem., 1972, 394, 197.
G. J. Bullen and P. R. Mallinson, J.C.S. Dalton, 1973, 1295.
J. S. Merriam and K. Niedenzu, J. Organometallic Chem., 1973, 51, C1.
H. M. Seip, R. Seip, and K. Niedenzu, J . Mol. Structure, 1973, 17, 361.
165
II:C-CHz
I
\
MeN, ,NMe
B
c1
(70)
and angles are: r(BN) 1.413(3), r(CN) 1.455(2), r(BC1) 1.770(4) A; LNBN
110.8(3)", LBNC 108.6(3)", and LNCC 105.7(3)'.
Some novel boron-containing heterocycles (71), (72; R1 = OMe, OEt, or
NH2; R2 = H or Me) have been obtained by the action of guanylurea,
guanylurea O-alkyl ethers, and biguanides with B(OMe), in MeOH or
MeO'
OMe
B(OH), in H20.308The products were characterized by i.r. and U.V. spectra,

thermal decomposition, and hydrolysis reactions.
Reactions of bis(dimethy1amino)phenylborane and aromatic diamines or
tetramines give polycyclic systems of considerable hydrolytic stability.309
Thus PhB(NMe& and 3,3'-diaminobenzidine give (73).
(73)
The reaction of diborane with 2-aminobenzonitrile gives, depending upon

the temperature, 2-cyanophenylamine-borane, bis(2-cyanopheny1amino)borane, and the naphthalene derivative (74) by loss of hydrogen. At more
elevated temperatures the product is a substituted borazine (75).310
H
308
A. N. Maitra and D. Sen, J. Inorg. Nuclear Chem., 1972, 34, 3643.
310
W. L. Cook and K. Niedenzu, Synth. Znorp. Metal-org. Chem., 1972, 2 , 267.

A. Meller and G. Beer, Monatsh., 1973, 104, 1055.
166
(75)
Treatment of BCI, with 1-aminoanthracene or 4-chloro- or 4-bromo-laminonaphthalene produces the new boron heterocycles (76) and (77;
Y = C1 or Br).311
Y
(77)
(76)
Condensation reactions between a-amino(or hydroxy)-benzenecarboxyacids (or amides) and B(NMe,),, PhB(NMe,),, or PhBCI, give organoboron
heterocycles (78) containing a carbonyl group in a /3-position to an annular
(78)
boron atom (where X = NH or 0; Y = NH or 0; 2 = NMe, or CI;

R = NMe, or Ph).,12
Interaction of (Me,N),BCI with NN-dimethyl-a,w-diamines yields
primarily l,3-dimethyl-2-dimethylamino-diazaboracycloalkanes
(79 ; n = 2
I--(CHZ),
I
MeN
\ B /NMe
I
NMez
311
312
(79)
B. Frange, Bull. SOC.chim. France, 1973, 2165.
W. L. Cook and K. Niedenzu, Synth. Inorg. Metal-org. Chem., 1973, 3, 229.

167
or 3).313 The reactions were carried out in refluxing n-hexane, and the yields
were 65% (n = 2) and 35% (n = 3).
Treatment of Na+BH,CN- in dry Et20 with HCl in 1 :1 ratio yields H,,
NaCl, and a mixture of polymeric cyanoboranes (BH,CN),. G.1.c. separation
of these yielded fractions of n = 4-10, but with only small amounts of the
macrocycles with n > 7. I.r., mass spectral, and llB n.m.r. data on (BH2CN),,
the most abundant species, were consistent with the structure (80).314
2-Methyl-l,3,2-dioxaborolan(81) may be prepared by the reaction of

BMe, and ethylene glycol at 380 C:
BMe,
+ (CH,OH),
--+ (81)
+ 2CH,
This previously ill-characterized compound was subjected to mass spectral,

i.r., n.m.r., and vapour-pressure studies.315
A six-membered-ring system consisting of one boron, three carbon, and
two oxygen atoms is found in the structure of meso-pentane-2,4-diol borate
(82).316The 5 carbon atoms are close to planarity, and the boron atom is
surrounded by three oxygens in an almost equilateral triangle. Two molecules

are linked by hydrogen bonds (length 2.80 A).
Tri-n-propanolamineborate N(CH2CH2CH20),Bcrystallizes in the hexagonal space group R3 [a = 13.798(6), c = 6.058(4) A; 2 = 3). The molecule
possesses a three-fold symmetry axis, and the six-membered rings adopt the
313
314
P. J. Busse and K. Niedenzu, Synth. Znorg. Metal-org. Chem., 1973, 3, 23.

B. F. Spielvogel, R. F. Bratton, and G. G. Moreland, J. Amer. Chem. SOC.,1972,94,
8597.
315
D.W.Webster, F. Longoor, and L. Barton, Synth. Znorg. Metal-org. Chem., 1973,3,
als
S . Kuribayashi, Bull. Chem. SOC.Japan, 1973,46, 1045.
115.
168
chair conformation. The transannular B-N distance is only 1.67 (6the
sum of their covalent radii of 1.58 A).317
Cleavage of di-t-butylsulphane by dihalogeno-organoboranes leads to the
formation of borothiins (83; R = Bun or Ph), according to:
2RBX2
+ 3Bu:S
-+ (83)
+ 6ButX
(X = C1,Br, or I).318
The trimeric metathioboric acid molecule (HSBS), crystallizes in the
monoclinic point groupP2,/c [ a = 13.949(6),b = 4.133(2), c = 17.532(8)A;
S
1
/I= 114.76(3)'; 2 = 41. The six-membered ring (84) is very nearly planar,
with r(BSring) 1.803(5), r(BSexocyclic) 1.813(6) A, and bond angles within
the ring of 130' (LSBS) and 110" ( LBSB).319
Electron-diffraction studies show that dimethyl- and dichloro-l,2,4trithia-3,5-diborolan (85; X = Me and C1) both possess a structure which is
very nearly
Trialkylthioboranes and 2-aminoethanethiol react to give a new class of

compounds, based on the -B-S-CH2CH2-NHunit, (86; X = Ph,
Et,N, or PrgN.322
Thioboranes react exothermally with trialkoxystibines at room temperature
PH2--0
'BSEt
3HzC
'CH2-S
C H 2 4
+ (BunO)3Sb
__+
(EtS),Sb
/'
+ 3HzC
>BoBun
'CH2-S
(88 % yield)
(EtS)*B
317
318
31e
s20
s31
sa2
+ (BunO),Sb
(EtS),Sb
Scheme 3
+ (Bu"O),B
(92% yield)
Z. Taira and K. Osaki, Inorg. Nuclear Chem. Letters, 1973, 9, 207.

M. Schmidt and F. R. Rittig, Z. anorg. Chem., 1972, 394, 152.
W. Schwarz, H. D. Hansen, H. Hess, J. Mandt, W. Schmelzer, and B. Krebs, Acta
Cryst., 1973, 29B, 2029.
H. M. Seip, R. Seip, and W. Siebert, Acta Chem. Scand., 1973, 27, 15.
A. Almenningen, H. M. Seip, and P. Vassbotn, Acta Chem. Scand., 1973, 27, 21.
R. H. Cragg and A. F. Weston, J.C.S. Dalton, 1973, 1054.
169
to give the corresponding alkoxyboranes and tri(alkylthio)stibine, which

can be separated by di~tillation,3~~
e.g. as shown in Scheme 3.
Mehrotra et al. have prepared a large number of new heterocyclic boron
derivatives, e.g. (87), (88; A,B,C,D = H), (88; A,B,C = H, D = Me),
(88; A,B,C,D = Me), and (89; A,B,C,D = H), (89; A,B,C = Me, D =
H).524
A number of derivatives of 4-methyl-l,3,Zdithiaborolan (90; R = Cl,
Ph, SEt, NEt,, or NHBu) have been prepared (e.g.for R = C1, from propene1 ,Zdithiol and BCI,). They were characterized by llB n.m.r., molecular
weight, and mass spectral data.a25For R = Ph and NMe,, mass-spectral
fragmentation patterns were discussed in detail.
A number of triselenadiborolans (91 ;R = I, Me, PryPh, or cyclo-C,H,,)

may be prepared by the treatment of organo-boranes or organo-BI, derivatives with red selenium.32s
The crystal structure of the previously known compound (h5-C,H,)Fe(CO)
[(CHNMe),BH,] shows unequivocally that the molecular structure is (92).327
The new heterocyclic silane (93) can be prepared from lY4-dilithio-octaphenyltetrasilane and dichloro(dimethylamino)borane.328It is a white,
333
324
325
326
3~
82s
R. H. Cragg, M. Nazery, and A. F. Weston, Inorg. Nuclear Chem. Letters, 1973, 9,

497.
S. K. Mehdra, G. Srivastava, and R. C. Mehrotra, J . Organornetallic Chem., 1973,
47, 39.
R. H. Cragg, J. P. N. Husband, and A. F. Weston, J.C.S. Dalton, 1973, 568.
W. Siebert and F. Riegel, Chern. Ber., 1973, 106, 1012.
W. M. Butler and J. H. Enemark, J . Organornetallic Chem., 1973, 49, 233.
E. Hengge and D. Wolfer, Angew. Chem. Internat. Edn., 1973, 12, 315.
170
crystalline solid, very sensitive to both oxygen and moisture, and slightly
soluble in benzene.
The action of B,(NMe,), on TiBr, yields a dinuclear species [B,Br,(NMe,),TiBr3]2,32g
Magnetic data and i.r. and electronic spectra are consistent with
the formulation (94).
Compounds containing B-S Bonds.-E.s.r.

spectra of "BS and l0BS in
their ground (3C+) states were measured in solid neon and argon matrices at
4 K.%*The following magnetic parameters were obtained: l1BS:gI12.0016(1),
81 1.9942(1); AII(llB) 853.3(3), Al(llB) 766.7(3) MHz.
H,S reacts with BX, (X = CI, Br, or I) to give the new substitutionproducts
BX2SH, BX(SH),, and B(SH),( HX).331These are unstable and cyclize to
(BSSH), or (BSX),. In the case of BBr, the ratios of reactants, and the
temperatures, can be controlled to yield any one of the 3 initial products in
high yield, so that either (BSSH), or (BSBr), may be obtained rapidly and
selectively. (BSCI), can best be prepared by dissolving (BSSH), in liquid
BCI,, and (BSI), by the action of H2S on solid BI,.
A vibrational assignment has been proposed for the molecules BX2SH
(where X = C1, Br, or I), and a normal-co-ordinate analysis was carried out,
using force-constant data derived from BX2CIsystems.332
Stoicheiometric quantities of KSR B2H6 give (in THF solution) the
thermally stable salts K+[RS(BH,),]-. Treatment of these with anhydrous
acids, B2H6, or I2 gives ,u-RS-B,H, in moderate yield,333thus:
K[EtS(BH,),]
+ 41,
toluene
P-EtS-BsHs
+ &Hz + KI
Rapid donor-acceptor bond-breaking and halogen-redistribution reactions

occur in solutions of Me,S,BX, a d d u ~ t s . ~
Relative
,~
rates of donor-acceptor
bond-breaking are: BF, > BF,Cl > BFCI2 > BCI, > BBr, > BI,. Halogen
redistribution gives large amounts of the non-fluorine-containingmixed boron
trihalide adducts, including Me,S,BCIBrI. Fluorine, however, is incompatible
with heavier halogens in these adducts, and only small amounts of Me2S,BF2Cl
and Me2S,BFC12are present at equilibrium; no evidence was found for
fluoro-bromo- or -iodo-adducts.
329
330
331
333
333
334
M. R. Suliman and E. P. Schram, Inorg. Chem., 1973, 12, 923.

J. M. Brom jun. and W. Weltner jun., J . Chem. Phys., 1972, 54, 3379.
J. Bouix and P. Hillel, Canad. J. Chem., 1973, 51, 292.
J. Bouix, M. Fouassier, and M. T. Forel, J . Mol. Structure, 1973, 15, 103.
J. L. Mielcarek and P. C. Keller, J.C.S. Chem. Comm., 1972, 1090.
M. J. Bula and J. S. Hartman, J.C.S. Balton, 1973, 1047.
171
BS, molecules (formed by heating ZnS-B mixtures) may be trapped in
neon matrices at 4 K.335Transitions due to theA2111.tPII,and B2Cz+- X211,
systems may be observed and these, together with matrix- and gas-phase i.r.
data, lead to the following molecular constants for 11BS2:B2)3:, To24 072,
v1 516; A211,, To 13 766, A, -263, ~1 506, ~2 311, ' ~ 1535;
3
X211,, A, -440,
vl 510, v2 120, v3 1015 (all figures in cm-l).
Boron Nitride and Metal Borides.-A new high-precision volumetric adsorption apparatus has been
to determine the energies of interaction
of Ne, Ar,Kr, and Xe with hexagonal BN at 273 K.
New mixed borides of Hf and Mo (Hf,Mo,B) and Zr and Mo (Zr,Mo,B)
have been prepared and characterized as K-borides by X-ray methods.337
The hafnium species will dissolve up to 14 atom% A1 at 1400 "C.
A new monoboride phase (CrB) has been detected in alloys prepared at
relatively low temperatures together with a chromium-rich phase which has
not yet been ~ h a r a c t e r i z e d .Investigations
~~~
in the Cr-B-C system show
that mutual solubility of the Cr carbides and borides is insignificant up to
1000 "C.Carbon/boron substitution in Mn2,C, extends almost to Mn2&,B3.
The complex borides V0.,Ru,.,B and Ni,.,Ru,,,B have been obtained for
the first time-they crystallize with the FeB-type structure, by contrast with
Fe2.2Rho.sB and Fe~.2Ir0.sB,which have the Fe3B structure. The stabilizing
influence of a number of metals on these was investigated.339
Amorphous, non-stoicheiometric 'Ni,B' is produced by the addition of
NaBH, to Ni(OAc), solution. The product contains excess Ni, which reacts
on heating to produce crystalline Ni3B.340
A detailed study of the B-Sc system has shown341that ScB, and ScB,, can
be prepared by the B reduction of Sc203at 1800 " C , 1600 "C, respectively,
(the latter at a higher B:Sc ratio). No evidence was found for ScB, or ScB,.
Crystallographic data have been reported for the tetragonal rare-earth
borides RCo,B, (where R = La, Nd, Sm, Gd, Tb, Dy, and Y). The La and
Y compounds crystallize in the ThCr,Si,-type structure.a2
The optimum temperature for the preparation of ruthenium borides from
the elements is 1200-1300 OC,with optimum times of 1,4, 10, 30, 70 h for
Ru,B3, RullBs, RUB^,^, Ru2B3,and RUB,, respectively.343
The crystal structure of Mo~-,B~(where x M 0.20) was investigated using
X-ray powder diffraction.344The crystal is hexagonal, with the space group
335
336
337
338
339
340
341
342
343
344
J. M. Brom jun. and W. Weltner jun., J. Mol. Spectroscopy, 1973, 45, 82.
R. N. Ramsey, H. E. Thomas, and R. A. Pierrotti, J . Phys. Chem., 1972, 7 6 , 3171.
P. Rogl, H. Nowotny, and F. Benesovsky, Monatsh., 1973, 104, 182.
G. Papesch, H. Nowotny, and F. Benesovsky, Monatsh., 1973, 104,933.
P. Rogl and H. Nowotny, Monatsh., 1973, 104, 943.
G. Bliznakov, P. Peshev, and G. Gyurov, Doklady Bolg. Akad. Nauk, 1972, 25, 1209.
J. Etourneau, J. P. Mercurio, R. Naslain, and P. Hagenmuller, Colloq. Znt. Cent. Rech.
Sci., 1972, 429.
K. Niihara, T. Shishido, and S . Yajima, Bull. Chem. SOC.Japan, 1973, 46, 1137.
G. V. Samsonov and V. A. Kosenko, Zhur. priklad. Khim., 1973, 46, 1171.
T. Lundstrom and I. Rosenber, J. Solid-State Chem., 1973, 6 , 299.
112
P6,lrnrnc [a = 5.2026(2), c = 6.3489(3) A]. The structure may be described
in terms of the stacking of two-dimensional boron nets and highly defect
metal layers. There are 2 types of molybdenum atom, and the environments
of the B, Mo(l), and Mo(2) atoms are shown in ( 9 3 , (96), and (97),
respectively.
(95)
The magnetic properties of the rare-earth tetraborides have been measured.=, PrB, is ferromagnetic, MB, (where M = Nb, Sm, Gd, Tb, Dy, or
(96)
No) are antiferromagnetic, while ErB, and YB, are metamagnetic.
The crystal structures of two complex ternary borides W21r3BGB(x m 1)
and Mo21rB, have been determined. The phase Mo2.,Irzm5B5
is isotypic with
IB- B\
B
B-B
(97)
s46
K. H. J. Buschow and J. H. N. Creyghton, J . Chem. Phys., 1972,57, 3911.

173
the former, but in Mo,IrB, there are B, units present. The phases (Cr, Ru)B
and (Mo, Ru)B have the FeB- and CrB-type structures, respectively, and
(Mo, R u ) ~ B
is ~isotypic with Ta,B,. The structural principles for borides in
the range 40-60 atom % B were discussed.346
Paramagnetic resonance measurements have been performed on the semiconducting compound EUB6.347
Y2ReB6 has orthorhombic symmetry (space group Pbam or Pba, ;a = 9.175,
b = 11.550, c = 3.673 A). The B atoms lie at the centres of trigonal prisms
formed by metal atoms, and themselves form networks of five-, six-, and
seven-membered rings.348
The crystal structure of CeCr2B, has also been determined.349The space
group is orthorhombic, Immm (a = 6.560, b = 8.318, c = 3.102 A; 2 = 2),
and the structure is of a new type, in which the B atoms form a framework of
corrugated fourteen-membered rings.
New ternary borides RCoI2B6 (R = Y or C1) have been prepared by
arc-melting in the R-Co-B systems, and characterized by X-ray powder
diffraction.350
The synthesis and X-ray identification of the new .r-borides Cr-131r-loB6,
Mn,-161r-7B6, Fel~15.&1~,.6B~,
and CO,~~I~,,B, have been reported.351
MB1, compounds may be prepared from M20, and crystallineor amorphous
boron in the temperature range 600-1450 "C, when M = Y, Tb, Dy, Ho,
Er, Tm, Tb, Lu, or Zr.352A detailed study was made of their electrical
properties.
Enthalpies of the dodecaborides MBrz (M = Zroe6Yo.4,Er, or U) were
determined between 1300 and 2200 K by a drop-calorimetric technique.353
Data were all fitted to a function of the type:
Hzl
- HZO8= kT + k'T2 - k"T-l - k"calmo1-l
The crystal structure of AlBe0.8B24.2(i.e. approx. AlBeB,,) shows that the

boron atoms are arranged in the same type of lattice as that found in tetragonal boron I, with Be atoms replacing some of the boron atoms on a random,
statistical basis. The aluminium atoms are situated in tetrahedral holes, each
hole being formed by 4 icosahedral B,, units. The A1 atoms are in general
not situated exactly at the hole centres.354
A single-phase erbium hectoboride (i.e. in the MB,o-loo range) has been
prepared and characterized as ErB65~4(by electron microprobe analysis)
346
347
348
349
350
351
352
353
354
P. Rogl, F. Benesovsky, and H. Nowotny, Monatsh., 1972, 103, 965.

H. Hacker, J. Magn. Resonance, 1972, 8 , 175.
Yu. B. Kuz'ma and S. I. Svarichevskaya, Soviet Phys. Cryst., 1972, 17, 569.
Yu. B. Kuz'ma and S. I. Svarichevskaya, Soviet Phys. Cryst., 1973, 17, 830.
K. Niihara and S. Yajima, Chem. Letters, 1972, 875.
P. Rogl and H. Nowotny, Monatsh., 1973, 104, 1325.
Yu. B. Paderno and V. V. Odintsev, Elektron, Str. Fix. Svoistva Tuerd. Tela, 1972, 2 ,
112.
R. W. Mar and N. D. Stout, J. Chem. Phys., 1972, 57, 5342.
K. Krogmann and H. J. Becher, Z . anorg. Chem., 1972, 392, 197.
174

or Er, .o*o.lB653--0 (by chemical analysis). The electron microprobe analysis
also confirmed the single-phase nature of the species.355
Structures of transition-metal borocarbides have been reviewed, in particular those of yttrium, i.e. YB,C,, YB,C, YBC, and YBo&, in a general
article on carbide structures.356
Lanthanides (La, Ce, Pr, Nd, Sm), when heated with a boron-carbon
mixture to 20OO0C, give two types of borocarbide~.~~'
All gave tetragonal
LnC,B,, but only La and Ce also gave LnC,B,.
2 Aluminium
General and Analytical.-The deformation characteristics of a monocrystal of
aluminium in the [112] direction have been
Edta titration of A1 in A1 alloys may be carried out using N-phenylanthranilic acid as precipitant.359
Chromazurol S complexes have been used360in the spectrophotometric
determination of aluminium.
Sensitivity enhancement of the fluorometric determination of aluminium is
obtained by the addition of surfactants to the metal complex solution.361
Amounts of A1 down to 5 x
g could be determined.
Aluminium forms a violet 1 :1 complex with Arsenazo I11 in the pH range
2-8, having characteristic absorptions at 550 and 583 nm. Examples of the
use of this complex for the photometric microdetermination of Al in calcite
were given; the sensitivity of this method is 0.01 ,ixg ml-1.362
A method for the analysis of oxygen in pure aluminium has been
described,363using activation analysis by means of charged particles, rather
than prays.
The effect of changes in co-ordination (from 4 to 6 , with oxygen ligands)
upon the 2s and 2p ionization energies of A1 is to shift these by about 2 eV.364
This effect is much greater than that observed for X-ray emission spectroscopy (for K, emission energy), and therefore ESCA is preferable to X-ray
emission spectroscopyfor the determination of co-ordination number.
Aluminium Hydrides.-Thermal
decomposition of NaAlH, proceeds by
the following stages: (i) melting of NaAlH, (185-190 "C), (ii) decomposition
M. C. Nichols and R. W. Mar, Inorg. Chem., 1973, 12, 1710.
H. Nowotny, Angew. Chem. Internat. Edn., 1972,11, 906.
357 L. Ya. Markovskii, N. V. Vekshina, and Yu. D. Kondrashev, Zhur. priklad. Khim.,
1972,45, 1183.
358 V. Gautchenko, M. Stasi, and P. Azou, Compt. rend., 1973,276, C, 563.
359 J. Endo and M. Sato, Japan Analyst., 1972, 21, 1348.
360 H. Nishida and T. Nishida, Japan Analyst., 1972, 21, 997.
361 N. Ishibashi and K. Kina, Analyt. Letters, 1972, 5, 637.
362 V. Mikhaylova, Acta Chim. Acad. Sci. Hung., 1973, 76, 221.
363 B. Viallatte, Compt. rend., 1972, 275, C, 1407.
364 C. J. Nicholls, D. S. Urch, and A. N. L. Kay, J.C.S. Chem. Comm., 1972, 1198.
355
356
175
to Na3NH6 (250-255 "c),(iii) decomposition of Na,AlH6 to NaH (275285 "C), and (iv) decomposition of NaH (425-430 0C).365
The reaction of NaAlH, with 2-dimethylaminoethanol has been followed
The main products were NaAlH(OR),
by conductivity
and NaAlH,(OR), (R = OCH,CH,NMe,). The trihydro-derivative was not
stable.
Methods for the synthesis of the Ca, Sr, and Ba salts of AlH; have been
explored. Although it is possible to displace one AlEt; ion from Ba(AlEt,),
with LiAlH,, the insolubility of Ba(AlH,)(AlEt,) effectively prevents the
reaction from proceeding to Ba(A1H4)2.367
The most effective method of
preparing the latter is by allowing the individual hydrides to react in ether
solvents. Thermal disproportionation occurs with Sr(AlH,),, to give AlH, and
sr3(A1H6)2*
Raman and i.r. data have been obtained for the AlH; ion (with Li+,
Naf, or Et,N+ cations) and for the GaH; ion (with Lif, Naf, or K+ cations),
in the solid phase and in solution (in EtzO, Me,O, THF, or 1,2-dimethoxyThe solution data for the AlH; systems were interpreted in terms
of 3 distinct species: tightly and loosely bound aggregates, and ion pairs. No
solvent co-ordination to AlH; was detectable. A vibrational analysis of
MH; (M = B, Al, or Ga) was carried out, and it showed an unusual sequence
for the M-H stretching force constants: BH; > GaH; > AlH;.
The torsional modes of motion of the AlH, ion in the lithium and sodium
salts have been studied by inelastic neutron scattering and they appear to
occur at higher frequencies than those in other systems.36Q
A study of the solubility diagram of the NaAlH,-diglyme (DG) system
reveals370the existence of three compounds : NaA1H4,3DG, NaAlH,,DG
(melting incongruently at -29, 44 ' C , respectively), and NaA1H4,2DG
(melting congruently at 15 "C).
The equivalent conductances of THF solutions of LiAlH,, NaAlH,,
(Bu,N)AIH,, and LiBH, were measured over a wide concentration range
(0.5 moll-l-1
x lo-' mol 1-1).571Thedatawereconsistentwith the following
conclusions: (a) (Bu,N)NH, and LiBH, are ion-paired, with the ions in
intimate contact, and (b) LiAlH, and NaAlH, species are present as solventseparated ion-pairs. Thermodynamic data confirm this finding for LiAlH,,
but suggest that a proportion of the NaAlH, ion pairs are in intimate contact
at 25 "C.
365
V. A. Kuznetsov, N. D. Golubeva, and K. N. Semenenko, Doklady Chem., 1972,205,
366
J. MachAEek, B. chsensw, and K. Abrham, Coll. Czech. Chem. Comm., 1973,38,343.

V. V. Gavrilenko, Yu. N. Karaksin, and L. I. Zakharkin, J. Gen. Chem. (U.S.S.R.),
1972, 42, 1555.
A. E. Shirk and D. F. Shriver, J. Amer. Chem. Soc., 1973, 95, 5904.
F. P. Temme and T. C. Waddington, J.C.S. Farada-v 11, 1973, 69, 783.
T. N. Dymova, Izuest. Akad. Nauk S.S.S.R., Ser. khim., 1972, 2108.
E. C . Ashby, F. R. Dobbs, and H. P. Hopkins jun., J. Amer. Chem. SOC.,1973, 95,
2823.
599.
367
368
369
370
371
176

Up to 30 % of a sample of SF, may be reduced to H2Sby a slurry of LiAIH,
in Et20over a period of one week. Although incomplete and slow, this is one
of the few recorded instances of the room-temperature decomposition of
SF,. 372
Conductometric titrations of ZnI, with LiAlH, in Et20 or THF are indicative of the formation of species of the type Zn[ZnI,(AlH,),,].373
Two new preparations of pure L&AlH, have been
from
LiAlH,
LiH in the presence of AlEt, as catalyst, or from LiH AlBr,.
LI,AlH, belongs to the orthorhombic space group P2,/rn, with a = 7.892(10),
b = 8.096(10), c = 5.650(10) A.
LiAI2H7has been prepared by a new method, according to the equation:
7LiH
+ 2AIC1, -+
LiA12H,
+ 6LiCl
X-Ray powder-diffraction patterns for LiAI2H, were indexed on the monoclinic system [a = 7.490(15), b = 15.570(15), c = 7.775(15) A;
=
108.80(15)0]. The thermal decomposition of Li2AlH7(giving A1 and Li,AIH,)
was also
The complex borohydrides K [Al(BH,),] and K[AICl(BH,),] differ from
Al(BH,), in not being spontaneously inflammable in air.376
The compound Et,0,AI(A1H4)3is prepared by the reaction of LiAlH, with
AIC13 in Et20 at -90 'C, followed by filtration of the precipitated LiCl and
pumping at
Thermal decomposition of this compound commences at ca. 100 "C,and is complete below 200 ' C . The following route was
suggested :
+ 9HE
Et2O,Al(AlHJ, 4 Et,O,AlH, + 3A1

EtaO,AlH, + EtZO
A1
QH2
The molecular structure of [Me2AIH], has been determined by gas-phase

electron diffraction.378The data are consistent with a model of DZhsymmetry (98), and the relevant structural parameters are r(A1C) 1.947(3),
r(AIHbr)1.676(19), r(AlAl) 2.617(6), r(CH) 1.117(5) A; LCAlC 1 18.5(0.9)',
and LAlHAl 102.6(1.6)'.
372
D. K. Padma, A. R. V. Murthy, W. Becker, and J. Massonne, J. Fluorine Chem.,
373
R. Bluke, V. Breick, and L. Liepina, Lafv. P.S.R. Zinat. Akad. Vestis., Kim. Ser.,
1972, 2, 113.
1973, 16.
374
975
376
377
378
J. Mayet, J. Trauchaut, and S. Kovacevic, Bull. SOC.ckim. France, 1973, 503.

J. Mayet, J. Trauchaut, and S. Kovacevic, Bull. SOC.chim. France, 1973, 506.
K. N. Semenenko and 0. V. Kravchenko, Russ. J. Inorg. Chem., 1972, 17, 1084.
P. Claudy, J. gtienne, and R. Bonnetot, Rev. Chim. rninPrule, 1972,9, 511.
A. Almenningen, G. A. Anderson, F. R. Forgaard, and A. Haaland, Acta Chem.
Scand., 1972,26, 2315.
177
Studies have been made379 of the reducing properties of aluminium

sesqui-(2-methoxyethoxy)hydride A12H3(OCH,CH200CH3), on a variety
of organic systems.
A 'H n.m.r. investigation of various mixtures of PEt, and chloroalanes
shows that the only adducts occurring in these systems are those with 1 :1
stoicheiometry Et ,O,AIH,C1,,.3so
A model olefin polymerization catalyst hitherto formulated as '[(h5C5H5),TiAIEt2],' has been
on the basis of n.m.r., mass spectral,
molecular weight, and analytical data, to be [(C,H,)(C,H,)TiHAIEt,], with,
presumably, the H atom bridging the Ti and A1 atoms.
Compounds containing Al-C and Al-Si Bonds.-A calculation, from mass
spectrometric measurements, has been made of the dissociation energies
(D:,atom) of AIC, (1104 f 21 kJ mol-l), AI,C, (1507 f 25 kJ mol-l), and
AIAuC, (1418 f 21 kJ m ~ l - l ) . ~ ~ ~
Experiments
the heats of mixing of trimethyl- and triethyl-aluminium
indicate that AHd(l)(the enthalpy of dissociation of the dimer in the liquid
phase) of the former is 19.4., f 0.3, kcal mol-l. This compares well with a
calculated value derived by analogy with hydrocarbon systems.383
The crystal structure of K[AIMe3(CN)]has been determined-it is monoclinic, space group C2/c [a = 19.902(7), b = 9.211(4), c = 9.615(4) A;
p= 107.74(5)'; Z = 81. In the anion, the A1-Me distance is 1.971(7)
(average), with A l - C N 2.047(7) &-this
lengthening being attributed to
the electron deficiency in the Al-CN bond.384
Electron-diffraction studies on dimethyl(cyclopentadienyl)aluminium
show that the ring is bonded in h3-fashion (99), with r[AIC(l)] 2.14(1),
02
Me
(99)
r[AIC(2)] 2.48(2), r[AIC(3)] 2.96(4), r(A1-C,H,)

2.13(1), and r(A1-CH,)
1.413(3) A?85
Gas-phase electron diffraction has been used to determine the molecular
structure of dimethylaluminium methoxide trimer [Me,Al(OMe)],, Figure
15.3861.r. and Raman spectra of this compound and its -OCD, analogue are
370
380
381
383
384
385
386
0. KiiZ, B. Chsenslq?, and 0. Strouf, Coll. Czech. Chem. Comm., 1973, 38, 842.
J.-P. Laussac and J.-P. Laurrent, J. Chim. phys., 1973, 70,417.
F. N. Tebbe and L. J. Guggenberger, J.C.S. Chem. Comm., 1973, 227.
C . A. Stearns and F. J. Kohl, J. Phys. Chem., 1973,77,136.
M. B. Smith, J . Phys. Chem., 1972,76, 2933.
J. L. Atwood and R. E. Cannon, J . Organometallic Chem., 1973, 47, 321.
D. A. Drew and A. Haaland, J.C.S. Chem. Comm., 1972, 1300.
D. A. Drew, A. Haaland, and J. Weidlein, Z . anorg. Chem., 1973, 398,241.
178
Figure 15 The molecular structure (lengths/& angles/') of [Me,AI(OMe)],

(Reproduced by permission from 2. anorg. Chem., 1973, 398, 241)
consistent with the presence of puckered, six-membered A1,0, ring skeletons
of C, or C2symmetry.387
Two novel compounds containing Al-Mo covalent bonds have been
and A12Me6, e.g.
isolated from the reaction of (h5-C5H5)MoH2
Evidence has been obtained from lH and l9F n.m.r. spectroscopy and by
determination of hydrolysis products for a number of fluorocarbonaluminium complexes such as Li [AI(C6H,C1)H,F], Li [A1(C6H,HCI)H,F],
and Li [AI(C,F2H2Cl)H2F].These arise in reactions between LiAlH, and
chloropolyfluoro-benzenes and -toluenes.3sg
388
G. Mann, A. Haaland, and J. Weidlein, 2. anorg. Chem., 1973, 398, 231.

R. A. Forder, M. L. H. Green, R. E. Mackenzie, J. S. Poland, and K. Prout, J.C.S.
Chem. Comm., 1973, 426.
R. S. Dickson and G. D. Sutcliffe, Austral. J . Chem., 1973, 26, 63, 71.

179
A mass spectrometric determination of the dissociation energies (D:)of
gaseous Al, (149 f 14 kJmol-l), AlSi (225.5 f 30kJmol-l), and AlSiO
(996.3 f 20 kJ mol-l) has been made.390
Compounds containing Al-N
Bonds.-Alkaline
tetra-amido-aluminate
and -gallate crystals may be prepared by means of ammonothermal synthesis. In the MAI(NH,), series (M = Na, K, or c s ) the structures are built
up from Al(NH,), tetrahedra and M+ ions [r(AlN) 1.85 A average], while
NaGa(NH,)4 is isotypic with NaAl(NH,),.391
A review has appeared on eight-membered cyclic compounds of Al, Ga,
In, and Tl.392
The ammonia adduct of calcium bis(tetra-amidoaluminate), Ca [Al(NH,)4]2,NH,, crystallizes in the monoclinic space group 12/c (a = 10.189,
b = 9.897, c = 12.151 A; ?!, = 98'36'; 2 = 4). The Al(NH,),.group is approximately tetrahedral [r(AlN) 1.85 A; r(NH) is variable in the range
0.67-1.12 A].393
The crystal structure of Me,Al,NCMe shows that the crystals are orthorhombic, space group Pnma; a = 6.617(3), b = 7.821(4), c = 16.135(7)A;
2 = 4.394The dimensions are shown in Figure 16.
Figure 16 The molecular structure (lengths/A,angles/") of (CH3),Al(NCCH3)

(Reproduced by permission from J. Organometallic Chem., 1973, 51, 105)
The structure of H,Al,NMe, as revealed by electron diffraction is as shown
in Figure 17. The Al-N bond distance is shorter than that in Me,Al,NMe,,
390
391
392
393
394
C. A. Stearns and F. J. Kohl, High Temperature Sci.,1973,5, 113.

P. Molinie, R. Brec, J. Rouxel, and P. Herpin, Acta Cryst., 1973, B29, 925.
J. Weidlein, J. Organometallic Chem., 1973, 49, 257.
P. Palvadeau, M. Drew, G. Charlesworth, and J. Rouxel, Compt. rend., 1972, 275, C ,
881.
J. L. Atwood, S. K. Seale, and D. H. Roberts, J. Organometallic Chem., 1973, 51, 105.
13
180
Figure 17 The molecular structure (lengths/& angles/') of H3AIN(CH3),

(Reproduced by permission from Acta Chenz. Scand., 1972, 26, 3928)
and longer than that in CI,A1,NMe3.395An electron-diffraction study of the
last molecule396gave the following parameters: r(CH) 1.121(25), r(NC)
1.516(12), r(A1N) 1.945(35), r(AlC1) 2.121(4) A; LNAlCl 104.9(0.7)',
LAlNC 112.6(1.5)". With the exception of r(A1N) all of the bond lengths
were more accurate than those determined by X-ray crystallography.
Tensimetric titrations between HMe,AI and NMe,, together with solution- and gas-phase molecular weight studies and lH n.m.r. spectral data
on trimethylamine-dimethylalaneH,Me,AI,NMe,, establish that it is a discrete compound, existing as an equilibrium mixture of monomer and moreassociated species.397
The presence of a six-membered ring of alternating A1 and N atoms in the
structure of dimethylamino-alane (Me,NAlH,), has been confirmed by
single-crystal X-ray measurement.398The ring is in the chair conformation
with r(A1N) 1.93(3) A; LAlNAl 115(2)', and LNAlN 108(2)'.
Trimethylaluminium-methylaminedecomposes at ca. 50 *C to give CH, and
cis- and trans-cyclotri-~-methylamido-tris(dimethylaluminium) (Me2AINHMe),.399 N.m.r., vibrational, and mass spectra were reported. The
crystal structures of cyclotri-p-methylamido-tris(dimethyla1uminium)[cis(A) and trans-(B)], and of cyclodi-p-dimethylamido-bis(dimethyla1uminium)
(C) have been determined.400(A) is rhombohedral, of space group R3 (a =
9.983 f 0.004 A; a = 104'39' f 3'), and contains six-membered (AlN),
rings in the chair conformation, r(A1N) 1.940 f 0.005, r(A1C) 1.973 f
0.005, and r(NC) 1.804 =t 0.010 A. (B) is monoclinic, of space group C2/c
395
3s6
3s7
3Q8
3Q9
400
A. Almenningen, G. Gundersen, T. Haugen, and A. Haaland, Acta Chem. Scand.,

1972, 26, 3928.
A. Almenningen, A. Haaland, T. Haugen, and D. P. Novak, Acta Chem. Scand., 1973,
27, 1821.
0. T. Beachley jun. and J. D. Bernstein, Inorg. Chem., 1973, 12, 183.
IC. N. Semenenko, E. B. Lobkovskii, and A. L. Dorosinskii, J. Struct. Chem., 1972,
13, 696.
K. J. Alford, K. Gosling, and J. D. Smith, J.C.S. Dalton, 1972, 2203.
G. M. McLaughlin, G. A. Sim, and J. D. Smith, J.C.S. Dalton, 1972, 2197.

181
(a = 11.897 f 0.008, b = 15.904 f 0.012, c = 9.778 f 0.007A; ,!=
l
10950 f 3); the molecular dimensions are the same as in the cis-isomer (A),
but with the skew-boat conformation. (C) is monoclinic, space group P2Ja
( a = 12.770 f 0.012, b = 8.104 f 0.007, c = 7.655 f 0.009A; /3 =
11739 f 3); it contains four-membered (AlN), rings, having approximate
DZhsymmetry, r(A1N) 1.958 f 0.005, r(A1C) 1.950 f 0.008 A.
A [bis(dimethylamino)alumino-oxy]dimethylamino-carbene complex results when iron pentacarbonyl reacts with tri~(dimethy1amino)alane.~~~
The compound is dimeric, as determined by lH n.m.r. data, and it is formulated as containing a four-membered Al,N, ring system (101). The formation
of the complex is thought to occur via nucleophilic attack of one aminogroup of the alane on a carbonyl carbon of Fe(CO),.
The extraction of hydroxothiocyanato-complexesof A1 or Ga by tributyl
phosphate (TBP) is more efficient than when no OH groups are present.
The extracted complexes may be formulated as [M(OH)(NCS),,3TBP],, with
the TBP co-ordinated to the metal, and -NCS bound via N (these last two
conclusions coming from i.r. data).402
A crystalline trimer, formulated as (102), results when [Et,Al(NPh,)], is
heated at 110 0C.403During the reaction ethane is lost. The reaction of the
trimer with AlCl, at 80 C in benzene substituted the ethyl groups, giving
the chloro-analogue of (102).
Etsdl-N
401
402
*03
pha
W. Petz and G. Schmid, Angew. Chem. Internat. Edn., 1972, 11, 934.
M. Sh. Zhambulova, S. S. Korovin, V. M. Klyuchnikov, and I. A. Apraksin, Rum. J .
Inorg. Chem., 1972, 17, 1316.
H. Hoberg, Annalen, 1972, 766, 142.
182
Et,Al(NPh,) reacts with aldimines R2CH=NR1 to produce a number of

substituted aluminium heterocycles based on the structure (1 03).404
Ph
I
Yellow, crystalline monomeric complexes R,MQ (R = Me, Et, or Bu';

M = Al, Gay or In; Q = quinolin-8-olate anion) have been isolated and
characterized by elemental analyses, i.r. , electronic, n.m.r., and mass
spectrometry.405The formation of these complexes is accompanied by a reduction in the reactivity of the M-C bond, and n.m.r. chemical shifts
can be rationalized on the assumption that M-C bond electron density
could be delocalized using s- and d-orbitals of the metal.
Alizarin Blue complexes of Al, Ga, and In chlorides have been synthesized
for the first time (complexing to the metal occurs via both the 8-hydroxyquinoline and a-hydroxyanthraquinone moieties.40s
1 :1 and 2: 3 complexes of aluminium isopropoxide with bifunctional,
terdentate Schiff bases (formed by condensation of o-hydroxyacetophenone
with hydroxyalkylamines) are formulated as Al(OPri)(SB) and Al,(SB),,
respectively, where SB is the dianion of the Schiff base.407*408
Molecular
weight determinations indicate that the former are dimers (104), the latter
monomers (105).
404
405
*06
407
408
H. Hoberg and A. Milchereit, Annalen, 1972, 766, 146.

B. Sen and G . L. White. J . Inorg. Nuclear Chem., 1973, 35, 497.
B. E. Zaitsev, N. P. Vasil'eva, B. N. Ivanov-Emin, and A. I. Ezhov, Russ. J. Inorg.
Cfiern., 1973, 18, 196.
J. P. Tandon and R. N. Prasad, Z . Naturforsch., 1973, 28b, 63.
J . P. Tandon and R. N. Prasad, Monatsh., 1973, 104, 1064.
183
,R3
AR4
R3
Compounds containing A1-0 or Al-S Bonds.-Mass spectrometric measurements on A10 systems have yielded the following dissociation energies (D,")
for A10 (1 18.6 f 2.5 kcal mol-l) and A1,O (249.0 f 5.6 kcal mol-l). The
first ionization potentials are 9.53 eV (A10) and 8.20 eV (Al,0).409
An independent measurement of the atomization energy of A1,O (251.6 f
4 kcal moI-l) is in agreement with this; in addition the atomization energy
of AlSiO was quoted as 252 f 8 kcal m 0 1 - l . ~ ~ ~
Salts of the new aluminyl cation A10+ have been prepared by the reactions
(in HF solution):
AlOCl
+ SbF, -+ A10+SbF;,A10+Sb2F;l
AlOCl
+ BFs -+ AlO+BFi etc.
and
etc.
v ( A l 0 ) is found in the i.r. spectrum at ca. 650 cm-l?ll These salts are relatively stable thermally, e.g. A l O + B Q gives AlOF BF, starting at ca.
85 "C, while A 1 0 + s b F ~is stable to 270 "C,when an analogous decomposition occurs. The X-ray powder-diffraction pattern of the latter salt
indicates that the unit cell is body-centered, has cubic symmetry (a = 10.17 f
0.02 A), and is isomorphous with the corresponding 02 and NO+ salts.
A TDOA-MO calculation has been carried out for the hypothetical
Al0;- ion in order to compare behaviour in the isoelectronic series A10:-,
SiO:-, and Ge0,4-.412
Aluminium alcoholates may be used to obtain Al,O, containing
wt % of impurities.413
X-Ray diffraction analysis of the thermal decomposition products of
D. L. Hildenbrand, Chem. Phys. Letters, 1973, 20, 127.

K. R. Thompson, High Temperature Sci.,1973, 5 , 62.
411 A. V. Pankratov, A. N. Skachkov, 0. N. Shalaeva, and G. M. Kurbatov, R u m J.
Inorg. Chem., 1972,17, 47.
412 S. P. Dolin, B. F. Shchegolev, and M. E. Dyatkina, J. Struct. Chern,, 1972,13, 904.
*la V. A. Smirnov, A. G. Kolenshenko, A. D. Chicharova, and R. K. Nikolaev, Monokrist. Tekh., 1972, 6 , 218.
409
184
Inorganic Chemistry of the Main-grozip Elements
AlQC1 and hydrated A1203shows that for the former the y- and x-modifkations of A1,0, are formed, whereas the latter gives y-, 0-, and ~ r - A l , o , . ~ ~ ~
Aerosols of A,O, may be obtained by thermal decomposition of the
corresponding alcoholate or AlCl,
H20!15
In solid solutions of A1203in Fe203,the crystallographic parameters a and
c decrease with increased A1 content. At the limit of solid solution (23.6
mole% A1203),the following are the values: a = 4.9806 f 0.0002 A, c =
13.568 f 0.002 A.416
The relative efficiencies of different transient forms of alumina as catalysts
for the dehydration of isopropyl alcohol have been measured.*17 The specific
activities were in the following sequence: q-w y- > 8-w 6- > K - A ~ , O ~ .
Heats of adsorption of water vapour on q-Al,O, have been determined by
means of a Tian-Calvet microcalorimeter at temperatures between 25 and
740 0C.458
Rates of adsorption of H,TeO, and H3P04on alumina have been studied
under varying pH conditions at 25 0C.419The experimental data were interpreted in terms of a multi-stage reaction, dominated by dissociative processes on the alumina. The assumed reaction of surface ions with anions in
solution was &rdorder in relation to acids, suggesting that the loose surface
complexes have unrestricted orientation of anions.
1.r. spectroscopicinvestigation of the products of chemisorption of toluene
on alumina shows that aluminium benzoate is the chief product above
200 oC.420This compound is also formed by the adsorption of benzaldehyde
cr benzoic acid, and confirms the oxidizing character of Al,O, surfaces.
Kinetic measurements on reactions of Li, Na, and K carbonates and hydroxides with Al,O,
that the rates of aluminate formation are in the
order Lif > Na+ > K+ for carbonates, and Na+ > K+ > Li+ for hydroxides.
The reaction of KAlO, with H2SO4has been examined.422At SOi-:AI
ratios between 0.1 and 1.0, Al(OH), is formed; from 1.0 to 2.0 an insoluble
basic salt of aluminium is produced, while in the range 2.0 to 4.0 a normal,
soluble double sulphate results.
Comparison of the standard free energies of formation at 298 K of
corundum, diaspore, boehmite, gibbsite, and bayerite leads to the following
selected values for free energies of formation (AH,O,,,): diaspore -219.5 f
0.5, boehmite -218.7 f 0.2, gibbsite -275.3 f 0.2, bayerite -274.6 f 0.1
kcal r n 0 1 - l . ~ ~ ~
414
*15
417
418
41e
430
422
423
V. I. Zhelankin, N. D. Dronova, and Yu. V. Oboznenko, Russ. J. Inorg. Chem., 1972,

17, 315.
J. L. Gass, F. Juillet, and S. J. Teichner, Bull. SOC.chim.France, 1973, 429.
G. PCrivet and R. Lafont, Compt. rend., 1972, 275, C, 1021.
H. Bremer and J. Ghetsch, Z . anorg. Chem., 1973,395, 82.
G. Della Gatta, B. Fubini, and G. Venturello, J. Chim. phys., 1973, 70, 64.
L. JaiimoviC, J. StevoviC, and S. VeljkoviC, J . Phys. Chern., 1972, 76, 3625.
M. Deflin, G. Cornier, M. Baverez, and J. Bastick, Compt. rend., 1973, 276, C, 623.
E. K. Belyaev and V. F. Annopol'skii, Russ. J . Inorg. Chem., 1972, 17, 1078.
S. V. Gevorkyan, D. G. Aslamya, S. T. Kostanyan, and L. A. Khachatryan, Russ. J .
Inorg. Chem., 1972, 17, 808.
G. A. Parks, Amer. Mirteralogist, 1972, 57, 1163.
Elements of Group IIf
185
A number of complexes [ e g . (106), (107; X = F, CI, or Br)] have been

characterized which contain M-CO-AlX,
or M-CO-BX,
They
all show an intense v(C0) band below about 1600 crn-l.
__
CP
COB%
(107)
(106)
Proton chemical shifts in aqueous solutions of AllI1 nitrate, perchlorate,

and sulphate have been measured over a range of temperatures, and the
effects of hydrolysis and addition of acid have been studied in detail. These
arise from changes in the interactions between the bulk water and three
different environments, viz. [AI(OH2),I3+ itself, the second hydration sphere
of this cation, and the broken-water structure around the anion.425
The intensity of the 27Aln.m.r. signal for aqueous solutions of chelates
with hydroxy-carboxylic acids (e.g. tartaric, mandelic, malic, citric) depends
markedly on the pH of the soIutions.426This is interpreted in terms of polymerization of the chelates, which results in dipole-dipole coupling between
the various 27Alnuclei.
27Al n.m.r. spectra of Al(ClOJ, dissolved in mixtures of H 2 0 and trimethyl phosphate (tmpa) show separate signals due to [Al(H@)6l3+,
[Al(H,0)5(tmpa)]3+, and trans-[A1(H,0)4(tmpa),].427
A number of double isopropoxides of lanthanides with A1 have been
prepared, by the reactions:
LnC1,,3PriOH
+ 3KAl(0Pri),
j .
Ln[Al(0Pri),ls
+ 3KC1
(Ln = La, Pr, Ce, Nd, Sm,Gd, Dy, Ho, Er, Yb, Lu, Y, or Sc) and:
Ln(OPri),
+ 3Al(OPri),
4 Ln[A1(OPri)k),
(Ln = Gd, Ho, or Er).428

Thermolysis of diethyl(tripheny1siloxy)aluminium leads to the interchange
of Et and Ph groups:429
Et
Ph&-O-AlEt3
-+
Ph2Si-O-Al
Et
434
425
436
427
420
/Ph
Et
I
I
-+ P h - S i - O A l P h n
Et
J. S. Kristoff, N. J. Nelson, and D. F. Shriver, J. Organometallic Chem., 1973,49, C82.

A. D. Joy, T. D. Smith, and J. R. Pilbrow, Austral. J. Chem., 1973, 26, 1889.
D. Canet, J. J. Delpeuch, M. R. Khaddar, and P. Rubini, J. Magn. Resonance, 1973,
9, 329.
R. C. Mehrotra, M. M. Agarwal, and A. Mehrotra, Synth. Znorg. Metal-org. Chem.
1973, 3 , 181.
V. V. Pankratova, L. P. Stepovik, I. V. Lomakova, and L. A. Pogochina, J . Gen.
Chem. (U.S.S.R.),1972,42, 1740.
186
The starting material was obtained from triphenylsilanol and triethylaluminium.

lH n.m.r. data on the compounds R5AI2ZM in aromatic hydrocarbon
solvents can be explained on the basis of donor-acceptor dinuclear complexes of the type [R,AlZM][AlR,] (R = Et or Bui, Z = 0, M = Na or
K ; R = Et, Z = 0 or NPh, M = Li; R = Et, Z = S , M = Na; or R =
Et or Bui, Z = 0, M = C S ) . ~ At
~ O higher temperatures an alkyl-exchange
reaction occurs via a cyclic intermediate.
The dimethylaluminium sulphinate Me,AIO,SMe has been prepared from
Me,AIBr and Ag0,SMe.431 1.r. and Raman spectra were reported and partially assigned.
The stability constants of 1 :1 and 1:2 aluminium formate complexes are
3.6 f 0.5 and b2 58 f l.432
The neutral acetylacetonate complex of A1111 reacts with picric acid in 1:1
benzene-ethyl alcohol, giving the cationic complex [(acac),Al(H,O),]+(pi~rate)-.4~~
Tris(tropolonato)aluminium(rrr) crystallizes in the monoclinic space group
C2/c1 [a = 10.855(12), b = 10.214(6), c = 17.719(13)A; /3 = 112.71(10)0].
The molecular symmetry is C2(2), but the distortion from an idealized
D3(32) symmetry is slight. The most significant feature of the A10, coordination sphere is the 48" twist angle (+) in (108), compared to 60' in a
regular octahedron. The relevance of this angle to barriers to trigonal twist
H
H
(108)
(109)
rearrangements was discussed. The averaged parameters (lengths/& angles/')

for an aluminium tropolonate are shown in
Mellite, A12[C,(COO),],1 6H20,
is tetragonal, with the space group I%/acd,
(a = 15.53 f 0.01, c = 23.19 f 0.01
Each A1 is surrounded octahedrally by water oxygen atoms.
T. Aoyagi, T. Araki, N. Oguni, and H. Tani, Znorg. Chem., 1973, 12, 817.
V. Gaiser, J. Weidlein, and E. Lindner, J. Organometallic Chem., 1973, 56, C1.
43a P. H. Tedesco, V. B. de Rumi, and J. A. Gonzalez-Quintana,J. Znorg. Nuclear Chem.,
1973,35,285.
433 M. M. Aly, J . Inorg. Nuclear Chern., 1973, 35, 537.
c34 E. L. Muetterties and L. J. Guggenberger, J. Amer. Chem. SOC.,1972, 94, 8046.
aC C. Giacovazzo. S. Menchetti, and F. Scordari, Acta Cryst., 1973, B29, 26.
430
431
187
with Alizarin Red S

A potentiometric study of complex formation of
(forming an 0-chelated complex) yields the values for the stepwise stability
constants of log Kf=O11.91 and log K;=O 6.71.436
The kinetics of formation of the 1 : 1 AlIII-methylthymol blue complex
may be followed spectrophotomeirica11y.437
Decomposition in air at 400 "C of mixed iron-aluminium oxalates leads
to a poorly organized mixed phase (NH,), [Fe,-,Al,(C,O,),].
At higher
temperatures this metastable phase crystallizes in two rhombohedra1 solid
solutions of the sesquioxides-one of high iron, one of high A1 content.438
3Li20,A1,0,,2Si02 is prepared by sintering Li2O,A1,0,,2SiO, with
Li2C03.439
X-Ray diffraction of glasses in the Na,O-Al,O,-SiO,
system shows that
the interatomic distances are rather similar to those found in the analogous
Li20-A1,O3-Si0, system.440
At high N a 2 0 concentrations in the Na20-Ca0-A1,0,-Ti0,-H,0
system,
the calcium aluminate 3Ca0,Al,0,,6H20 is formed?,,
A study has been made of the phase relationships in the system NaAlSi,O,CaA1,Si,0,-Na2C0,-H,0.442
A preliminary note443on the crystal structures of RbSiAlO, and CsSiAlO,
(prepared by hydrothermal synthesis) reports that both belong to the space
group Pc2,n, and lists unit-cell parameters for both systems.
Enthalpies of formation (from the oxides) of MgAl,04 and A12Si05
(kyanite and sillimanite) have been determined by oxide melt solution
calorimetry at 965 and 1173 K.444
Raman studies have been made on natural and a number of synthetic
MgA1,04 spinel crystals.445Deviations in Raman selection rules in the synthetic crystals can be ascribed to disordering in the Mg-A1 sites, and can be
useful in characterizing such crystals.
Phase relationships in Mg0-A1,O,-TiO2 have been
The following species were shown to be present: MgTi,O,, Mg,TiO,, Al,TiO,,
and MgAl,04.
Ca(NO,), and Al(N0,)3 react at 1000C to give 3Ca0,A120,; 12Ca0,7A1203;CaO,A1,0; Ca0,2A1,03; and Ca0,6A1203.447
A refinement of the crystal structure of 11Ca0,7Al,03,CaF2 confirms that
436
437
438
439
440
441
448
443
444
445
446
447
P. K. Govil and S . K. Banerji, J . Chinese Chem. SOC.,1972, 19, 83.

T. V. Mal'kova and V. D. Ovchinnikova, Russ. J. Znorg. Cliem., 1972, 17, 813.
A. Rousset and J. Paris, Bull. SOC.chim. France, 1972, 3729.
Z. S. Tkacheva and L. K. Yakovlev, Zzvest. sibirsk. Otdel. Akrzd. Nauk. S.S.S.R., Ser.
khim. Nauk., 1972, 73.
S. Urnes, Phys. and Chem. Glasses, 1972, 13, 77.
E. Schultze-Rhonhof, Z . anorg. Chem., 1973, 396, 303.
A. F. Koster van Groos and P. J. Willie, Amer. J . Sci., 1973, 273, 465.
R. Klaska and 0. Jarchow, Naturwiss., 1973, 68, 299.
J. A. Shearer and 0. J. Kleppa, J. Inorg. Nuclear Chem., 1973, 35, 1073.
L. M. Fraas, J. E. Moore, and J. B. Salzberg, J. Chem. Phys., 1973, 58, 3585.
P. Boden and F. P. Glasser, Trans. andJ. Brit. Ceram. SOC.,1973, 7 2 , 215.
V. Figusch and E. Kanchir, Silikaty, 1973, 17, 31.
188
the F- sites are only partially occupied and that Ca2+ions adjacent to filled
fluoride positions are displaced. No evidence was found to indicate an
ordered structure in a lower-symmetry space group.448
Mossbauer spectra of CaAI,,-,Fe,O,,
solid solutions with x < 4.8 show 3
resolvable quadrupole doublets arising from Fe3+ions in tetrahedral, trigonalbipyramidal, and octahedral sites. The first was preferred, however, as seen
by an analysis of the relative intensities.449
Phase relationships in the system Ca0-A1,0,-Fe0-Fe203 have been
Many liquid compositions in this system form glasses.
A single-crystal X-ray investigation of Ba13A12,Silo0,, shows the presence
of both SiO, and AIO, tetrahedral ~ n i t s . 4The
~ ~ structure consists of sixmembered-ring systems formed by condensation of, alternately, three SiO,
and three AIO, tetrahedra and three-membered-ring systems formed from
A10, units. Further condensation by other tetrahedra gives a three-dimensional framework.
The compound of approximate composition Ba0,AI,03,H20 has a structure analogous to that of sodalite, based on a framework of empirical formula
AlO,. The Ba atoms are distributed over a number of sites in the cavities,
which also contain the remainder of the A1 atoms. The latter are octahedrally co-ordinated, probably by a mixture of OH- and H,0.452
Substitution of A1 and Si by Ga and Ge ions in synthetic BaA1,Si20, and
SrAI,Si,O, has been studied.453The compounds can be obtained in either
monoclinic or pseudo-orthorhombic phases, with the former being more
stable for Ba compounds, and the latter for Sr.
The phase diagram of Ba0-Zr0,-A1,03 has been reported.454
The series LiA11-,Cr,02 was prepared from solid-state reactions of Li2C03
and (All--oCrz)203.455
Thermal stability and diffuse-reflectance spectra were
measured and the latter were analysed by the extended crystal-field theory.
Equilibria in the system AI,O3-SiO2-H,O have been studied with the
aim of establishing the stability limits of p y r ~ p h i l l i t e . ~ ~ ~
A compound of the composition +M00,,A1~0,,2SiO~is prepared by
heating the constituents at 1200 "C for 12 h.457X-Ray powder-diffraction and
i.r. data were reported.
Kaolin, A12Si,0,(OH),,, reacts with NiO between 900 and 1100 "C to
form the green spinel NiA1204, together with free SiO, and mullite,
448
449
450
451
452
453
454
455
456
457
P. P. Williams, Acta Cryst., 1973, B29, 1550.

F. P. Glasser, F. W. D. Woodhams, R. E. Meads, and W. G. Parker, J. Solid-state
Chem., 1972, 5 , 255.
J. A. Imlach and F. P. Glasser, Trans. and J. Brit. Ceram. SOC.,1973, 72, 221.
W.Gebert, Z. Krist., 1972, 135, 437.
A. H. M. Ahmed, L. S. Dent Glasser, and M. G. King, Acta Cryst., 1973, B29, 1166.
G. Gazzoni, 2. Krist., 1973, 137, 24.
M.T. Mel'nik, E. I. Ved', and N. G. Ilyukha, Izvest. Akad. Nauk. S.S.S.R.,Neorg.
Materialy, 1973, 9, 332.
H. P. Fritzer, E. Sliuc, and K. Torkar, Munatsh., 1973, 104, 172.
H. Haas and M. D. Holdaway, Amer. J. Sci., 1973, 273,449.
A. Ueno and Y. Kotera, Chem. Letters, 1973, 21.
Elements of Group 1.1
189
Al,Si,Q,,.458 An analogous reaction with CuO at 1000 O C gives the last two
products and C U A ~ , ~ , . ~ ~ ~
Yttrium aluminates are formed by heating Y203 Al,03 in the temperature range 9OO-IOOO 0C.460
The synthesis of the zeolites Linde A and faujasite has been studied using
phosphorescence spectroscopy and laser-Raman spectroscopy.461 The
results obtained were indicative of a zeolite crystallization in the solid gel
phase via condensation between hydroxylated Si-A1 tetrahedra.
A study of the Raman spectra of a number of natural and synthetic
zeolites
that these are not as informative as i.r. spectra, although
some characteristic differences were observed.
The crystal structure of the synthetic zeolite Na-PI, represented by the
formula Na,A1,Silo,12H,0, has been solved by X-ray methods.463It is closely
related to the gismondine-type framework.
The aluminosilicate framework in a number of zeolites, e.g. (Nal,Bao.5)30A130Si600192,1
.7(Na2,Ba)Cl2,72H,O, has been investigated by X-ray
methods.464
The crystal structure of vacuum-dehydrated zeolite 4A, Nal,A11,Sil,0,8,
has been determined.465The space group is Pm3m (cubic, a = 12.263 A),
and the framework structure is shown in Figure 18, with Na+ ions placed
statistically within each of the three kinds of sites.
The activation energy of the dehydration reaction :
is 12 kcal mol-l at 100 0C,466while thermal dissociation of the nitrate, with

release of nitrogen oxides, occurred at 180 "C (activation energy 37 kcal
mol-l). The final product obtained at 400-450 "C was Al,03,H20.
X-Ray studies on the structure of the pentanitrato-aluminate anion
[A1(N03),]2- show that both uni- and bi-dentate nitrate groups are present,
as shown in Figure 19.467
X-Ray diffraction patterns and t.g.a. results have been reported for the
precipitates obtained from Al,03,N,0,-H20 at 125, 150, 175, and 200 0C.468
4r8
459
460
4ea
463
464
465
466
467
468
M. Hassanein and S. El Sawy, 2.anorg. Chem., 1973, 396, 328.

M. Hassanein, Z . anorg. Chem., 1972, 392, 188.
M. V. Kniga, T. G . Mikhaleva, and M. N. Rivkin, Russ. J. Inorg. Chem., 1972, 17,
903.
B. D. McNichol, G . T. Pott, and K. R. Loos, J . Phys. Chem., 1972, 76, 3388.
C. L. Angell, J. Phys. Chem., 1973, 77, 222.
C. Baerlocher and W. M. Meier, 2. Krist., 1972, 135, 339.
R. M. Barrer and D. J. Robinson, 2. Krist., 1972, 135, 374,
R. Y. Yanagida, A. A. Amaro, and K. Seff, J . Phys. Chem., 1973,77, 805.
N. I. Yanakiev and D. Trenafelov, Doklady Bolg. Akad Nauk., 1972, 25, 1641.
0. Ya. Dyachenko, L. 0. Atovmyan, G. N. Shirokova, and V. Ya. Rosolovskii,
J.C.S. Chem. Comm., 1973, 595.
Kh. R. Ismatov, L. M. Bogacheva, R. Z. Karimov, A. P. Gazner, and M. T. Saibova,
R u s . J . Inorg. Chem., 1972, 17, 1324.
190
Figure 18 The molecular framework structure of vacuum-dehydrated Zeolite

4A
(Reproduced by permission from J. Chem. Phys., 1973, 77, 805).
Figure 19 The molecular structure (lengths/& angles/) of the Al(N0,);- ion

(Reproduced from J . C. S. Chem. Comm., 1973,595)
191
A solubility diagram has been constructed for the quaternary system
AI(NO~)~-MOO~-HNO~-H~O.~~~
The complex dehydration processes of potassium aluminium alum have
been followed by t.g.a., X-ray diffraction, and i.r. methods.470
The thermal decomposition of AI,(SO,),, 18H20 has been studied.471
Under Ar, loss of water occurs at 50, 80, 130, 200-300, and 450 O C (2, 4,
6, 5, and 1 mole, respectively), and the AI,(S04), gives y-A1,03 and SO, in
the region 700--900C. In the presence of H,, loss of water (14 mole)
occurs at 100-200 "C and (4 mole) 450 "C, with decomposition of A12(S04),
to amorphous Al,03 and SO, in the range 500-600 "C.
Solubility and tie-line equilibria have been studied for the system propan2-ol-H,O-AI2(S0,), at 5, 15, 25, and 35 OC.,',
The effect of temperature on
the phase diagrams is very small.
Solubility isotherms for the Rb,SO,-AI,(SO,),-H,O
system at 25 O C have
been obtained. The Al-Rb alum Rb2S04,A12(S04)3,24H20
is formed over
a wide concentration range.473
Mendozite, NaA1(SO4),,1 1H,O, crystallizes in the space group C2/c (a =
21.75 f 0.03, b = 9.11 f 0.10, c = 8.30 f 0.01 A; B = 92'28';Z = 4).The
principal structural units are (i) corner-sharing, infinite Na(O,H,O), octahedral chains with two 'winglike' SO, tetrahedra attached to each octahedron, having the composition [Na(H20),(S04),]3-; (ii) independent
[A1(H20),I3+ octahedra; and (iii) isolated A120 molecules. The average
Na(O,OH,), AI-0H2, and S-0 distances are 2.408, 1.878, and 1.473 A,
respecti~ely.4'~
The crystal structure of voltaite, K2Fe~1Fe~11Al(S04)12,18H20,
shows that
the mineral crystallizes in the space group Fd3c (cubic, a = 27.254 A). The
dominant structural feature is a continuous framework composed of
[Fe3+0,]octahedra, [Fe~~,Fe~f,o4(OH2),]
octahedra, and [K+O12]polyhedra,
linked by SO, tetrahedra.475This arrangement gives rise to 'cages' occupied
by disordered [Al(H,0)6]3+ octahedra.
The phase diagram (at 50C) of the system A12(S04),-ZnS0,-H,O has
been reported.476The existence of the double sulphate 3ZnSO4,2Al,(SO4),,36H,O was confirmed. This double sulphate is dehydrated with accompanying
formation of Zn and A1 sulphates, while thelatter is hydrolysed to AI(OH)SO,.
The i.r. spectrum of the double sulphate shows no co-ordination of SO,
groups, and it is therefore formulated as {[Zn(H,O),], [AI(H,0),],)(S04),.477
Phase formation in the TiO2-Al20,-SO,-H2O system in boiling 80%
46D
470
471
474
473
474
475
476
477
0. N. Krasnobaeva and I. N. Lepeshkov, Russ. J. Inorg. Chem., 1972, 17, 1498.

E. B. Gitis, N. Sh. Safiullin, E. F. Dubrova, V. F. Annopol'skii, and N. M. Panasenko,
Russ. J. Inorg. Chem., 1972, 17, 810.
A. K. Zapol'skii and I. I. Fedoritenko, Voprosy Khim. i Khim. Tekhnol., 1972,25,72.
0. Matsuda and A. Yoshida, Nippon Kagaku Kaishi, 1972, 1970.
V. G. Shevchuk and A. A. Maksimenko, Russ. J. Inorg. Chem., 1972, 17, 133.
J. H. Fang and P. D. Robinson, Amer. Mineralogist, 1972, 57, 1081.
K. Mereiter, Tschermak's Mineral. Petrograph. Mitt., 1972, 18, 185.
A. S. Moshinskii, Russ. J. Inorg. Chem., 1972, 17, 598.
A. S. Moshinskii, Rum. J . Inorg. Chem., 1972, 17, 1527.
192
Inorgrtiiic Chemistry of the Main-group Elements
sulphuric acid has been studied by t.g.a., X-ray diffraction, chemical analysis,
and electron microscopy. A complex sulphate of the form Ti02(0.1AI2O3)(1 .3SO3) was ~ h a r a c t e r i z e d . ~ ~ ~
The solubility isotherms of the systems A12(S0,)3-Li2S04-MnS04-H20479
and A12(S04)3-CdS04-H20480have been measured at 25 'C.
The compound LiAl(WO,),, not previously described, is produced by
heating the Li2W04-A12(W04),system?81 The X-ray diffraction pattern of
this species has been indexed in terms of the monoclinic system (a = 9.09,
b = 11.25, c = 14.74A; p = 90.37').
The thermal properties of AlPO4,2H2Ohave been s t ~ i d i e d . ~ ~ ~
The effect of water content on the formation of various A1 phosphates from
Al, Al,O,, or Al(OH), and H,P04 has been
A14(P4012)3
is easily
formed by secondary heat treatment only when the water content of the
primary product is < 10 % or >25 %.
The thermal decomposition of H, [Al(P04),],3H20 follows the scheme:484
235 "C
Al(POa)3
359 "C
f--
A12(HzP207)s
Al, Ga, and In trimetaphosphimates have been isolated from the systems
MC13-Na3(P30,N3H3)-H20, (M = Al, Ga, or In).485
M(BTO~)~,~H
(M~ O
= Al, Ga, or T1, n = 9, 7, or 3, respectively) and
In(OH)(Er0,),,2H20 decompose on heating to give the sesquioxides as final
products. All the intermediates were unstable except T10(Br0,).486
An analysis of the A2Z+-X2Z+transition of AlS has been made, and values
have been calculated for the vibrational and rotational levels in the A2C+
and X 2 Z + states.487
478
479
480
481
482
483
484
485
487
L. I. Bekkerman and I. N. Zabrodin, Russ. J . Inorg. Chem., 1972, 17, 1245.

A. A. Maksirnenko and V. G. Shevchuk, Russ. J. Inorg. Chem., 1973, 18, 296.
A. S. Karnaukhov, T. P. Fedorenko, and V. G . Shevchuk, Russ. J . Znorg. Chem., 1973,
18, 152.
M. V. Mokhosoev, E. I. Get'man, R. N. Isakova, and S. A. Pavlova, Rum. J. Inorg.
Chem., 1972, 17, 995.
A . G. Kotlova and N. I. Shchepochkina, Russ. J. Inorg. Chem., 1972, 17, 165.
M. Tsuhako, K. Hasegawa, T. Matsuo, I. Motooka, and M. Kobayashi, Chem.
Letters, 1973, 367.
V. F. Tikavyi, K. N. Lapko, A. N. Lobanok, A. N. Chivenkov, and A. A. Sokol'chik,
Vestsi Akad. Navuk. Belarusk. S.S.R., Khim. Navuk, 1972, 74.
I. A. Rozanov, V. R. Berdnikov, V. I. Sokol, and L. A. Butman, Izuest. Akad. Nauk
S.S.S.R., Neorg. Materialy, 1973, 9, 152.
B. Dusek, Sb. Vys. Sk. Chem.-Technol. Prazr, 1972, B14, 95.
H. Lavendy, J. M. Mahieu, and M. Becart, Canad. J. Spectroscopy, 1973, 18, 13.
193
X-Ray powder-diffraction data have been used to construct phase diagrams

for the pseudo-binary systems MIMIIIS,-ZnS (MI = Cu or Ag; MII1 =
Al, Ga, or In).488
The lattice constants a and c have been tabulated for CuAIS2,CuInS2, and
AgGaS2 crystals.48sThe following bond lengths were derived from these:
Al-S 2.239, In-S 2.517, and Ga-S 2.235 A.
Aluminium Halides.-Aluminium reacts with MgFz at steel-smeltingtemperatures to give a volatile subfluoride of aluminium. On condensation this disproportionates, giving A1 metal, which is then oxidized in air to the oxide
or suboxide of Al?90
The matrix-isolated i.r. spectrum of OAlF has been reported and
as follows: v2 386 cm-l, v3 1022 cm-l; v1 (Al-F stretching) was
not observed but was calculated to be at 675 cm-l.
Negative ions derived from AlF,, GaF,, InF,, and TlF, have been studied
by high-temperature Knudsen-cell mass spectrometry. F- was observed
from all 4 compounds, together with AIF,, GaF;, InF;, TlF;, and TIF;.492
The degree of dissociation (p) of AlFi- (considered to give AlF;
2F-)
in the system Li,AlF,-CaF, has been calculated493to be 0.40.
The electrical conductivities of LiF-AlF, and NaF-AlF, molten mixtures
were analysed in terms of MF-M,AlF, and M,AlF,-MAlF, eq~i1ibria.l~~
Despite these results, however, there is a considerable body of evidence
that the AlF; ion does not exist as such. Thus, thermodynamic measurements on the NaF-AlF, system suggest that there is only a weak interaction
between F- and AlF,, and that no clearly defined AIF; ions are present.495
Lattice-energy calculations on the hypothetical compound NaAlF, have
been carried
Some enthalpies of reaction were calculated between
compounds in the NaF-AlF, system.
A method has been developed for calculating stabilities of complex ions
in binary molten salt mixtures, using accurate enthalpy of mixing data as
bases.497It was possible to discriminate between two possible models for the
dissociation of molten cryolite :
Na,AlF,(l) -+3NaF(1)
or
Na,AlF,(I) -+ 2NaF(I)
488
4D1
4w3
493
496
497
+ AIF,(l)
+ NaAlF,(l)
M. Robbins and M. A. Miksovsky, J . Solid-state Chem., 1972, 5 , 462.

G. Brandt, A. Rauber, and J. Schneider, Solid State Comm., 1973,12, 481.
B. M. Nikitin, T. I. Litvinova, T. F. Raichenko, and V. A. Voronov, Russ. J. Inorg.
Chem., 1972,17,474.
A. Snelson, High Temperature Sci., 1973, 5 , 77.
F. Petty, J. L.-F. Wang, R. P. Steiger, P. W. Harlan, J. L. Franklin, and J. L. Margrave,
High Temperature Sci., 1973, 5 , 25.
J. Vrbenskh and M. Malinovsky, Coll. Czech. Chem. Comm., 1973,38, 659.
K. Matiaxovskg and V. Danlk, J . Electrochem. SOC.,1973, 120, 919.
J. L. Holm, Acta Chem. Scand., 1973, 27, 371.
J. L. Holm, Acta Chem. Scand., 1973, 27, 1410.
J. L. Holm, Inorg. Chem., 1973, 12, 2062.
194
Only the former is consistent with the enthalpy of dissociation (AHaiss) of

22 kcal and a degree of dissociation ( a ) of 0.31.
Using an accurate transpiration method, no reaction between AIF,(g)
and HF(g) was detectable at 1200 K.498
Phase diagrams have been constructed for the binary systems K,AIF,Na,AIF, and K,AlF,-Rb,AlF, using thermal analysis, d.t.a., and low- and
high-temperature X-ray diffra~tion.4~~
A continuous solid solution was found
in the K-Rb system, but in the K-Na system a compound 2K3AIF6,Na,AIF,
was detected, melting congruently at 954 'C.
The viscosities of Li3MF, and Na&F,, in the ranges 9oO-~100c,
1040-1 170 "C,respectively, have been measured.500
Rb and Cs hexafluoroaluminates are prepared in 90% yield by drying
and calcining a mixture of AlF3 and RbF or CsF in a 1:3 molar ratio at
980-1000 *C, 820-840 "C,respectively.501
The phase diagram of CS3A1F6-Li&F6 has been reported.502
Structural relationships in the compounds AI1B1I1F5 (AII = Cr, Mn,
Cd, or Ca; BIII = first-row transition element, Al, or Cia) have been
elucidated by a comparative study of their crystallographic data.503
New quaternary fluorides MIAgMIIIF,, where MI = M, Rb, or Cs,
MIII = Al, GayIn, or TI, have been reported and characterized by X-ray
powder diffraction, magnetic measurements, etc.504
1.r. spectra of the hydrated species MiM1I1F5,H2O, M1M1I1F4,2H2O
(MI = K, Rb, Cs, T1, or NH,; MII1 = Al, Gayor In), and their deuteriated
analogues can be interpreted as showing the presence of lattice, rather than
complexed, water. Hydrogen-bonding is stronger in the gallium species than
in either the A1 or In analogues.505
The crystallization surface of the 2A1,3Ca [I 6C1,6F ternary reciprocal
system has been determined;506as has the phase diagram of the 6Na,3BaY
2A1 11 6F system. In the latter the compound 3BaF2,2A1F3was detected.507
(J = 1 -+2) and 27A179Br
The quadrupole hyperfine structures of 27A135C1
(J = 0 4 1) have been measured, giving the following quadrupole coupling
constants: (AICI), eqoQ(27A1)= -29.80(50) MHz; eq0Q(35CI)= -8.60(10)
MHz; (AIBr), eq0Q(27A1)= -27.90(50) MHz, eqoQ(35Cl)= +78.78(20)
MHZ.~O~
T. B. Douglas and R. F. Krause jun., J. Res. Nat. Bur. Stand., Sect. A , 1973,77,341.
K. Grjotheim, J. L. Holm, and S. A. Mikhaiel, Acta Chem. Scand., 1973,27, 1299.
500 I. Votava and K. Matiagovsky, Chem. Zvesti, 1973, 27, 172.
501 S. M. Arkhipov, T. V. Revzina, and N. I. Kashina, Metody. Poluch. Khim. Reaktiv.
Prep., 1972, 24, 76.
502 M. Amcrasit, B. J. Holm, and J. L. Holm, Acta Chem. Scand., 1973, 27, 1831.
J.-M. Daud and A. Tressaud, Compt. rend., 1973, 277, C, 379.
5u4 B. Miiller and R. Hoppe, Z . anorg. Chern., 1973, 395, 239.
iio5
P. Bukovec, B. Orel, and J. Siftar, Monatsh., 1973, 104, 194.
M. A. Kuvakin and E. N. Evstifeev, Russ. J. Inorg. Chem., 1973, 18, 147.
M. A. Kuvakin, A. N. Sunin, and L. I. Talanova, Russ. J. Inorg. Chem., 1972, 17,
1459.
5 0 8 J. Hoeft, T. Torring, and E. Tiemann, Z . Nutrrrforsch., 1973, 28a, 1066.
408
400
195
A completely sealed-offC12 1 C1- electrode cell has been developed and used
to make a potentiometric study of the KCI-AlCl, system.509The pKvalue for:
2AlCl;
+ A1,CI; + Cl-
was found to be 7.83 f 0.02 at 300 'C. At very low pC1- (high C1- activity)
the addition of ZnII gave ZnClP, while at lower Cl- activities this dissociated
to ZnC1,
C1- (pK for this reaction was 2.15 f 0.04 at 300 "C).
During the volatilization of mixtures of BeCl, and AICl,, mass-spectrometric evidence was found for the presence of BeAlCI,, Be,AlCl,, BeAl,Cl,,
Be,Al,Cllo, and (in very small amounts) Be3Al,Cll, in the vapour. The
structures (1 10) and (111;n = 1,2, or 3) were proposed for these.510
The Raman spectra of MCI-AICI, melts (M = Li, K, or Cs) in the range

50-100 mol% of AlCl, have been observed.511 They may be analysed in
terms of the presence of AlCl,, Al,CI;, AI,C16, and higher polymers. It was
apparent that the AlCl; and A1,Cl; ions were interacting with M+, giving
vibrational perturbations.
Solubility isotherms (at 25OC) have been constructed for the systems
AIC13-LiCl-Et,0, AlC1,-LiC1-toluene, and AlBr,-NaBr-t~luene.~~~
1.r. spectra of the 1 :1 complexes of AlCl, or AIBr, with pyridines and
pyridine N-oxides have been interpreted513in terms of approximately tetrahedral co-ordination at the Al. Force constants were calculated using a simple
model in which the ligand is treated as a point mass. Typical observed wavenumbers are: AIBr3(2-picoline), v1 210, v2 450, v3 112, v4 395, v5 128, v6 80
cm-l, and the Al-N stretching force constant is 1.3 f 0.1 mdyn kl.
Simple 1:1 adducts of AlX, (X = C1 or Br) with S,N, have been reported
for the first time.514They are orange-red, crystalline materials, characterized
by their i.r. spectra and elemental (S,N, Al, C1, or Br) analyses.
a-PdC1, reacts with gaseous AI,CI, to give a deep-red gaseous complex
PdAl2C1,. The electronic spectrum of this is consistent with the formulation
(1 121.515
509
510
511
51a
613
514
515
J. H. von Barner and N. J. Bjerrum, Inorg. Chem., 1973, 12, 1891.

M. Binnewies and H. Schafer, Z . anorg. Chem., 1973, 395, 6 8 .
E. Rytter, H. A. a y e , S. J. Cyvin, and B. N. Cyvin, J. Inorg. Nuclear Chem., 1973,35,
1185.
A. E. Pruntsev, S. M. Arkhipov, and V. I. Mikheeva, Bull. Acad. Sci. U.S.S.R.,Div.
Chem. Sci., 1972, 2581.
D. H. Brown, D. T. Stewart, and D. E. H. Jones, Spectrochim. Acta, 1973,29A, 213.
C. H. Chan and F. P. Olsen, Inorg. Chew., 1972, 11,2836.
G. N. Papatheodorou, J. Phys. Chem., 1973,77,472.
14
196
A number of thermodynamic parameters have been calculated for the

reactions :
M,O,(c)
+ O.SAlZCl&)
-+ 2MOCl(c)
+ AlOCl(c)
(M = Nd or Sm). Thus, for M = Nb, AH,Ozgs = 8.7 f 0.3 kcal mol-l,

AS,,,, = 4.1 f 0.4 cal d e g l mol-l,
AHt298(NdOC1) = -247.1 f 0.3 kcal
mol-l; and for M = Sm, AH,Ozzss= 9.6 f 0.7 kcal mol-l, AS,.,,, = 9.3 f 1.2
cal deg-l mol-l, AHf0298(SmOCl)= -247 f 0.7 kcal ~ 0 l - l . ~ ~ ~
Formation of lanthanide ~hloride-A1~Cl,complexes enables a clean

separation of all adjacent lanthanide elements to be performed on a column
packed with glass beads.517
The reaction of aluminium borohydride with tetraethylammonium
chloride or bromide gives crystalline compounds (Et,N) [Al(BH,),X] (X =
C1 or Br).51sThese are readily soluble ill benzene, and could be characterized
by X-ray powder diffraction and i.r. spectroscopy. These confirmed the
presence of the anion shown, rather than a mixture of [AI(BH,),]- and
AlX;. When X = C1, v(AIC1) was seen at 495 cm-l.
Calculated values of 79Brnuclear quadrupole coupling constants in M79Br,
where M = 27Al,
69Ga, or l151n, increase in the series 27Al< 69Ga < l151n.
This trend parallels that found for the experimental values, although the
absolute values differ considerably from t h e ~ e . ~ l ~
Solution reaction caloriinetry has been used in order to obtain values
for the standard enthalpies of formation of aluminium(II1) bromide and
iodide, via the enthalpies of aqueous alkaline hydrolysis of these systems.520
Thus, AHf"zgs.ls(AIBi.,,cryst.)= -494.8 f 2.7 kJ mol-l, while AHfo298.15
(AlI,,cryst) = -280.4 f 2.6 kJ mol-l.
Dissociation constants of aluminium bromide,
AI,Br,
+ AlBr; + AlBr,
in n-heptane (7.24 x loaz3) and benzene (7.53 x loB1'), have been calculated from measurements of the dependence of electrical conductivities of
&Br, solutions upon c ~ n c e n t r a t i o n . ~ ~ ~
516
517
618
'19
520
621
M. Atchayya and V. V. Dadape, High Temperature Sci., 1973, 5 , 1.

T. S. Zvarova, Radiochem. Rndionrznlyt. Letters, 1972, 11, 113.
L. V. Titov, E. R. Eremin, and V. Ya. Rosolovsky, Izuest. Akad. Nauk. S.S.S.R., Ser.
khim., 1972, 1480.
P. Machmer, 2. Nuturforsch., 1972, 27b, 1271.
M. E. hnthoney, A. Finch, and P. J. Gardner, J.C.S. Dalton, 1973, 659.
M. Svestka, Coll. Czech. Chem. Comm., 1972, 37, 3831.
199
Potassium heptabromoaluminate KAl,Br, is monoclinic in the crystalline
phase, belonging to the space group P2Jc [a = 12.373(2), b = 10.822(2),
c = 14.444(3)A; /3 = 133.87'; 2 = 41. The A1,Br; anion consists of two
AIBr, tetrahedra sharing one corner, (1 13), with r(AIBrterminai) 2.252.32 A, r(A1Brbridge) 2.37, 2.43 h;, and LAlBrAl 109.3.522
The 81Br n.q.r. spectrum of (Al,Br,,benzene) shows 3 signals which are

interpreted as indicating a strong similarity with the structure of
pure A12Br6.523
Electromigration methods, together with i.r. and lH n.m.r. spectroscopy,
have been used to investigate complex formation in solutions of AlBr, in
esters (E). In the 1 :1 complexes, ionization gives mainly the species rA1,Br5,2E]+ E, and [AlBr,,nEr, but small amounts of [AIBr2,2E]+, [AlRr,]-,
and [AI,Br,,E]- also occur.524
Tertiary lamellar compounds can be prepared when graphite reacts with
AlBr,-Br, mixtures.525With Br, saturated with AIBr,, the compound has
the composition C,AlBr,,Br,. The lowest bromine content is found in C2*A1Br3,Bro.,, while a third, non-stoicheiometric composition can be obtained
at about cG6Br(AlBr3)o-2.A phase diagram has been determined for the
ternary system. Electrical resistivity measurements of these graphiteAlBr,Br, systems point to the ionization of all of the bromine molecules in the
ternary compounds, but it is not possible at present to determine whether
the formula is GBr-,(3A1Br3) or C~Br6-(3AIBr,)'-.
Equilibrium diagrams of SiCh and GeCI, with Al,Br, have been investigated by d.t.a.526
Calorimetric titrations show that AlzBra forms 1 :1 AlBr, adducts with
a-bromo-,qx-dibromo-, and a,a,a-tribromo-acetophenone and RCOPh
(K = Me, Pri, or PhCH2).527Heats of complex formation and equilibrium
constants were determined.
The quadrupole hyperfine structure of 27AP271was measured for the
522
583
E. Rytter, B. E. D. Rytter, H. A. Dye, and J. Krogh-Moe, Actu Cryst., 1973,B29,1541.
T.Okuda, Y. Furukawa, and H. Negita, Bull. Chem. SOC.Japan, 1972,45,2245.

Yu. A. Lysenko, V. V. Pinchuk, and A. A. Kuropatova, J. Gen. Chem. (U.S.S.R.),
jZ4
1972,42,2739.
6p5
526
T. Sasa, Y. Takahashi, and T. Mukaibo, Bull. Chem. SOC.Japan, 1972,45,2250,2657.

G.M. Kurchyumov, V. A. Molochko, and L. K. Agureeva, Russ. J. Inorg. Chem.
1972,17, 1206.
527
V. A. Smrchek, I. P. Romm, V. F. Traven, and B. I. Stepanov, Trudy Moskou. Khim.

Tekhnol. Znst., 1972,70, 22.
198

* following coupling
rotational transition J = 1 2 at 14 G H z . ~ ~The
constants were obtained: eqoQ(27Al)= -215.50(10) MHz; eqOQ(lz7I)=
-307.407 - 4.315(~ 8) f 0.100 MHz.
--+
Other Aluminium Compounds.-The

new tetragonal ternary tellurides
MMhTe, (M = Sr or Ba; M' = Al, Ga, or In), Ba,AI,Te,,, NaInTe,, and
KInTe, have been synthesized, and crystal parameters determined.529
A new, body-centred-cubic structure V,Al has been prepared from the
elements at high temperature and pressure.530
The phase Cu,Al, has a crystal structure of the partially filled NiAs type,
and CuAl has a structure which may be described as a vacancy variant of the
CsCl structure.531
Mass-spectrometric analysis of the species present in the vapour above an
Al-Cu alloy in the range 1157-1882 K has led to a value for the dissociation
energy of AlCu (AH; = 50.9 f 2.5 kcal m ~ l - l ) . ~ , ~
The dissociation energies (A:) for the gaseous metallic species AlAg and
AlAu have been obtained by Knudsen-cell mass spectrometry.533The values
were 180 f 9 and 325 f 13 kJ mol-l, respectively, in line with relative
bond strengths in the alloys. Similar data have been obtained by this technique for AlAu, (506.3 f 25.1 kJ mol-l) and AI,Au (460.2 f 20.9 kJ
m~l-l).~,~
YNiAI, and YNiAl, both belong to the space group Cmcm (a = 4.08,
b = 15.44, c = 6.62 A; a = 4.07, b = 10.13, c = 7.06 A, respectively). The
structures are related-YNiAl, contains series of columns of trigonal prisms,
of composition [Ni(Y,AI,)],, which are isolated from one another. The
YNiAI4structure contains similar columns, but these are now separated by
corrugated networks of A1 atoms.535
A study5,, of the Yb-A1 system reveals that the only intermetallic compounds formed are YbAl, (melting congruently at 136OOC) and YbAl,
(formed peritectically at 980 "C). Magnetic susceptibilities and lattice constants were determined for these phases in the temperature range -180 to
+550 ' C .
Oriented single crystals of CeAI, up to 3 cm long may be prepared by the
Czochralski method.537
528
52B
530
531
532
533
534
535
536
637
T. Torring, E. Tiemann, and J. Hoeft, Z . Naturforsch., 1973,28a, 1062.

E. R. Franke and H. Schafer, Z . Naturforsch., 1972, 27b, 1308.
J.-M. LCger and H. T. Hall, J. Less-Common Metals, 1973, 32, 181.
M. El Baragy, R. Szepan, and K. Schubert, J. Less-Common Metals, 1972, 29, 133.
J. Perakis, C. Chatillon, and A. Pattoret, Compt. rend., 1973, 276, C, 1357.
A. M. Cuthill, D. J. Fabian, and S. Shu-Shou-Sen, J . Phys. Chem., 1973,77, 2008.
K. A. Gingerich, D. L. Cooke, H. C. Finkbeiner, and C.-A. Chang, Chem. Phys.
Letters, 1973, 18, 102.
R. M. Rykhal, 0. S. Zarechnyuk, and Ya. P. Yarmolyuk, Souiet Phys. Cryst., 1972,
17, 453.
( a ) A. Palenzona, J . Less-Common Metals, 1972, 29, 289; (6) A. Iandelli and A.
Palenzona, ibid., p. 293.
M. Godet, E. Walker, and H.-G. Purwins, J. Less-Common Metals, 1973, 30, 301.
199
3 Gallium
General and Analytical.-Supercooled liquid Ga can crystallize in the
metastable 6-form at atmospheric pressure. 6-Ga belongs to the rhombohedral space group R3m, and the unit cell contains 22 atoms at 5 independent
special sites.538
Gallium(m) may be extracted, and quantitatively separated from ZnII,
moll-l) using 2-ethoxyfrom aqueous solutions (acid concentration &
carbonyl-5-hydroxy-l-(4-tolyl)-4-pyridone.539
A number of derivatives of pyridylazoaminophenol have been shown54oto
be suitable reagents for the spectrophotometric determination of Ga.
A method for the determination of GaIII has been devised which involves
co-deposition of Ga with Zn on a Pt electrode, followed by the recording of a
stripping voltammogram in a fresh ammoniacal solution-the Ga and Zn
appearing as clearly separated peaks (N.B. Ga is not deposited well on a Pt
electrode in the absence of, for example, Zn).541
Gallium forms a three-component complex with Catechol Violet and
quinine (having an absorption maximum at 680 nm) which may be used for
its photometric determination.542
Methylxylenol Blue has been used as a reagent for the spectrophotometric
determination of Ga.543Al, AsV, SbIII, BiIII, Zr, Th, FeIII, and PdII
interfere with the determination, but Al, Zr, and Th can be masked by the
addition of NaF, and FelI1 by adding ascorbic acid.
1-(2-thiazolylazo)-2-naphthol-3,ddisulphonic acid has been shown to be a
useful reagent for the spectrophotometric determination of Ga, In, and
TllI1 in the range 2-10mg, in the presence of foreign ions.544Ga and In
can be determined in each others presence.
The extraction system trioctylamine-aqueous NH,SCN solution can be
used to separate Ga from A1 and Fe by an extraction chromatographic
met hod.545
Gallium may be estimated in low-temperature coal ash by neutron activation analysis, with radiochemical separation.546Amounts in the range 1-10
p.p.m. were determined.
The presence of large amounts of Ga suppresses the extraction of T P ,
In, Zn, Co, and Se (small amounts) from aqueous acidic phases5*'
Compounds containing Ga-N Bonds.-The mixed nitride CaGaN may be
prepared by the reaction of Ca3N, and GaN or by the action of Ca,N, on Ga
538
639
540
641
542
543
544
545
546
547
L. Bosio, H. Curien, M. Dupont, and A. Rimsky, Acta Cryst., 1973, B29, 367.
M. J. Herak, B. Tamhina, and K. JakopEiE, J. Inorg. Nuclear Chem., 1973, 35, 1665.
S. I. Gusev and L. G. Dazhina, J. Analyt. Chem. (U.S.S.R.), 1972, 27, 1961.
S. Araki, S. Suzuki, and T. Kuwabara, Japan Analyst., 1973, 22, 708.
M. I. Shtokalo and L. V. Livadko, Zhur. analit. Khim., 1973, 28, 484.
J. Ueda, Nippon Kagaku Kaishi, 1972, 1422.
A. 1. Busev, Zhur. analit. Khim., 1972, 27, 2165.
G. I. Shmanenkova, Zhur. analit. Khim., 1972, 27, 2161.
R. Santoliquido and R. R. Roch, Radiochem. Radioanalyt. Letters, 1972, 12, 71.
Yu. A. Zolotov and V. I. Golovanov, Russ. J. Znorg. Chem., 1972, 17, 8 8 8 .
200
under an atmosphere of N,. It crystallizes in the space group P4/izmrn (a =

3.57, c = 7.55 A). The electrical conductivity of CaGaN is very high, and
metallic in nature.548
Continuous-wave and pulsed lH n.m.r. data have been obtained for solid
H3Ga-NMe, in the temperature range 63-300 K.549The activation energy
for rotation of the -GaH3 group was found to be 3.6 f 0.3 kJ mol-l(0.86 f
0.07 kcal mol-l).
The tricyclic pyrazolyl-dideuteriogallanedimer (N,C3H3,GaD& has been
characterized structurally by a single-crystal X-ray
The six-membered
Ga(N-N),Ga ring was shown to be present in the boat conformation (1 14).
Complex thiocyanatogallates [(pyH),Ga(NCS),] and
have been isolated from aqueous solutions, and [ (pyH)Ga(NCS)4] from a

methanolic solution.551The individuality of the complexes was confirmed
by chemical, i.r., and X-ray analyses.
Trimethyl- and triethyl-gallium(1Ir) react with NMe,X (X = CN, NCO,
NCS, or N3) to give complexes NMe,[R3GaX] (R = Me or Et) and NMe,[(K,Ga),X] (X = CN or N3 only). In the 1 :1 complexes, vibrational spectra
shoiv that the Ga-X bonding involves the C (X = CN), N (X = NCO),
or S (X = SCN) atom. In the 2: 1 cyanide complexes bonding occurs via
Ga-C and Ga-N, whereas in the 2: 1 azido-complexes, only the or-N atom
is bonded to the
Complex formation of GaIII with 2,2-bipyridyl and 1,lO-phenanthroline
has been studied by the competing reaction with Ag+ ions in an acetate
Formation constants of complexes are as follows: (bipy), & (3.45 f
0.73) x lo4, 16., (5.08 f 0.86) x lo7; (phen),
(3.84 f 0.24) x lo5, p2
(2.74 f 0.31) x lo9. Measurements of the same constants by competition
reactions with MnII gave results554which agreed with these within experimental error.
548
549
550
561
562
553
554
P. Verchier, R. Marchand, and J. Lang, Compt. rend., 1973, 276, C, 607.

M. B . Dunn and C. A. McDowell, Mol. Phys., 1972, 24,969.
D. F. Rendle, A. Storr, and J. Trotter, J.C.S. Chem. Commi., 1973, 189.
L. M. Mikheeva, A. I. Grigorev, and A. I. Tarasova, Russ. J. Itiorg. Chem., 1973, 18,
43.
K. Dehnicke and I. L. Wilson, J.C.S. Dalton, 1973, 1428.
F . Ya. Kulba, V. L. Stolyarov, and A. P. Zharkov, Russ. J. h o r g . Chem., 1972, 17,
57.
F. Ya. Kulba, V. L. Stolyarov, and A. P. Zharkov, Russ. J. Inorg. Chern., 1972, 17,
197.
201
The planar Ni complex containing the NN-ethylenebis(saIicyla1diminato)
ligand, [NiII(saen)], reacts with GaX, (X = C1 or Br) to form a 1 :1 adduct
represented as {GaX,[Ni(saen)],}+(GaX,)-. 1 :1 Adducts in which the
planarity of the transition metal is maintained are formed with InX, (X = C1
or Br), however.555
Investigation of the kinetics of decomposition of Ga or In azomethine
complexes shows that the gallium complexes are the more stable, and that Nsalicylideneaniline complexes are more stable hydrolytically than those of
N-(2-hydroxy-l -na~hthylidene)aniline.~~~
Compounds containing Ga-0 or Ga--S Bonds.-Auger and direct electron

spectra from Ga and Ga203show that the former signals are more sensitive
to chemical environment than the direct electron signals.557
A new allotropic form of GaO(0W) has been isolated which is orthorhombic and crystallizes in the space group Fddd (a = 10.140, b = 8.321,
c = 7.010
The Ga is six-co-ordinate, having 6 oxygen atoms arranged
in a distorted trigonal-prismatic manner (1 15).
E.m.f. investigation of the equilibrium:
yields a value for AH,& of -259.6 f 0.4 kcal mo1-1.559

The thermoelectric power and electrical conductivity of nearly stoicheiometric Ga20, polycrystals have been measured.560In the temperature range
650-900 K electron mobility increases with temperature, while for T >
900 K, band conduction occurs.
CaGa,04 belongs to the space group Pna, (&), with a = 10.189, b =
7.725, c = 9.032 A. The Ca2+ ions have irregular 7-8-co-ordination (by
655
558
557
558
559
M. D. Hobday and T. D. Smith, J.C.S. Dalton, 1972, 2287.

S. S. Lyapina, L. P. Shamaiko, A. V. Leshchenko, and E. P. Trailina, J. Gen. Chern.
(U.S.S.R.), 1972, 42, 2126.
G. Schon, J. Electron Spectroscopy, 1973, 2, 75.
P. Vitse, J. Galy, and A. Potier, Comnpt. rend., 1973, 277, C, 159.
J. V. Smith and D. Chatterji, J. Amer. Ceram. SOC.,1973, 56,288.
L. N. Cojocaru and I. D. Alecu, 2.phys. Chem. (Frankfurt),1973, 84, 325.
202
oxygen atoms), while Ga3+ is regularly tetrahedrally co-ordinated, and

r(Ga0) is 1.84 A.561The superstructure of BaGa,O, has been investigated by
single-crystal X-ray diffraction.562
Copper(rr) gallate CuGa,O, is thermodynamically stable at temperatures
>600 0C.563
Magnetic measurements and Mossbauer spectra show that the mixed
ferrigallate of copper CuFe1~,Ga,~,O4possesses an inverse spinel structure,
with approximately GO % of the gallium in A - ~ i t e s . ~ ~ ~
Gallosilicates of the approximate composition M20,Ga,0,,2Si0, (M =
Li, K, Rb, or Cs) have been prepared for the first time,565by heating mixtures of @a(OH), and alkali-metal disilicates in the temperature range 8001200 '6 for between 70 and 180 h. The X-ray powder diffractions of the Li
and K systems can be indexed on the hexagonal system (a = 13.60 =t 0.01,
c = 9.09 f 0.01 A for Li; a = 10.50 f 0.01, c = 8.51 f 0.01 8, for K).
The formation of phases Ga,0,,3M20,21W03 has been confirmed in the
systems M,W04-Ga,03-W03 (M = Rb or Cs), and they were characterized
by X-ray powder diffraction.566
The phase diagrams of the Ga20,-W03 and In,(WO,),-WO, systems
have been determined.567In,(WO,), melts incongruently at 1410 'C, and
has a reversible polymorphic transition at 255 'C.
The i.r. spectra of ordered spinels LiX1llY:rrO,
= Ga or In,
YIII = Cr or Rh) have been assigned,568with the help of GLi/7Liisotope
shifts. Most of the vibrations involve participation of the X and Y cations,
but the lowest-lying fundamental (ca. 220 cm-l) is assigned as a translational
mode of the XO, unit .
Roasting Ga with a rare-earth metal in a mufie furnace at ca. 750C
gives gallates with the garnet structure M,Ga,O,, (M = Y,Gd, or
Calculations of structure factors for garnets with previously deduced
distributions of ions have confirmed the structural formulae {Nd,.,Yb,&
[Yb,](Ga,)QI2 and {Pr3)[Lu,](Ga3)O12,i.e. the rare earths fill all of the
dodecahedra1 and octahedral sites.570
Spectrophotometric characteristics of UIV gallate complexes in methanol
and aqueous methanol have been investigated,571and successive instability
constants determined.
661
562
663
564
565
566
567
568
569
670
571
H.J. Deiserotli and H. Miiller-Buschbaun, 2. anorg. Chem., 1973, 396, 157.

H.-J. Deiseroth and H. Muller-Buschbaum, J. Inorg. Nuclear Chem., 1973, 35, 3177.
A. A. Slobodyanyuk, Yu. D. Tret'yakov, and A. F. Bessonov, Russ. J. Inorg. Chem.,
1972, 17,922.
J. Lopitaux, J.-C. Tellier, J. Foct, and M. Lenglet, Compt. rend., 1973, 277, C, 19.
A. S. Berger, T. I. Samsonova, and J. A. Porashina, Russ. J. Inorg. Chem., 1972, 17,
643.
S. Pavlova and M. V. Mokosoev, Russ. J. Inorg. Chem., 1973, 18, 138.
V. I. Karpov and I. B. Korotkevich, Rum. J. Inorg. Chem., 1973, 18, 301.
P. Tarte and J. Preudhomme, Spectrochim. Acta, 1973, 29A, 1301.
A. ha. Golub, S. M. Gozhdzinskii, and B. S . Khomenko, Inorg. Materials, 1972, 8,
1796.
L. Suchow and R. Mondegarian, J . Solid-state Chem., 1973, 6 , 553.
N. V. Chernaya and S. Ya. Shnaiderman, Russ. J . Inorg. Chem., 1973,18, 63.
203
The 50 "C solubility isotherm of the Ga,(S0,),-ZnS04-H20 system has

been measured.572
New mixed chlorosulphates MIGa(SO,Cl), (MI = Li or Na) have been
prepared by the reaction :
MIGaCl,
+ 4S0,
-+ MIGa(SO,Cl),
in liquid SO,. The compounds were characterized by X-ray powder diffraction and i.r. spectra (the characteristic bands of SO,Cl- were seen).573
Complex formation in the Ga3+-H2C20,-HC10, system has been followed
by amperometric titrations. Only the non-protonated complex [GaC204]+
exists, with an instability constant K[GaC,O,]+ = 8.8 x 10-7.574
X-Ray diffraction studies have revealed that [Ga2(OH)2(C14H17N3)2C12,H20contains hydroxo-bridged, octahedrally co-ordinated Ga atoms.
This is the first time that such a grouping has been found (Ga-Obridge distances are 1.908-2.017A). In addition, the Ga-CI distances were found
to be rather different from the usual values, and thus the concept of a constant Ga-Cl distance in octahedral GaIII complexes is not valid.675
Complex formation between GalI1 and 4-phenyl-7,8-dihydroxycoumarin
in solution may be followed spectrophot~metrically.~~~
The final product was
a 1:2 complex, the nature of which was dependent on pH, as shown in
Scheme 4.
Studies on the extraction of Ga from aqueous solutions to benzene solutions containing capric acid show that two hexameric gallium caprates,
[GaR2(OH>l6and [GaR,(H,O)],, are responsible for the extra~tion.5~~
Stability constants of complexes of Ga3+ and In3+ with Tiron (disodium
1,2-dihydroxybenzene-3,5-disulphonate)have been determined by the pHpotentiometric method.578
The crystal structure of AgGaS2 has been determined-the crystals are
tetragonal (space group I42d;Z = 4, a = 5.75722 f 0.00803, b = 10.3036 f
0.0002 at 298 K).579The G a - S distance is 2.276 f 0.001 A, while Ag-S
is 2.556 f 0.001 A, and LSGaS 111.1 f 0.1'.
Er,GaS, is orthorhombic, space group Cmc2 (a = 10.36, b = 13.12,
c = 6.40 A). The Ga is tetrahedrally co-ordinated by sulphur [r(GaS)
2.2s A1.580
Gallium thiophosphate, GaPS,, has a monoclinic crystal structure and its

space group is P2Jc [a = 8.603(4), b = 7.778(3), c = 11.858(5) A; /l=
135.46'; 2 = 41. The Ga and P atoms are each surrounded by 4 sulphur
572
573
574
575
576
577
578
579
A. S. Moshinskii, Russ. J . Inorg. Chem., 1973, 18, 152.

B. Van Dorpe, M. Drache, and B. Dubois, Compf. rend., 1973, 276, C, 73.
Yu. I. Mikhailyuk and V. I. Gordienko, Russ. J . Inorg. Chem., 1972, 17, 668.
K. Dymock, G. J. Palenik, and A. J. Carty, J.C.S. Clzern. Comm., 1972, 1218.
A. K. Kalra, H. B. Singh, and R. P. Singh, J . Inorg. Nuclear Chem., 1973, 35, 187.
H. Yamada and M. Tanaka, J. Znorg. Nuclear Chem., 1973,35, 3307.
R. P. Guseva and V. N. Kumok, Russ. J . Znorg. Chem., 1972, 17, 1680.
S. C. Abrahams and J. L. Bernstein, J . Chem. Phys., 1973, 59, 1625.
S. Jaulmes and P. Laruelle, Acta Cryst., 1973, B29, 382.
204
OH
/-2H+
r
Scheme 4
atoms at the vertices of distorted tetrahedra.581The Ga-S distances are in

the range 2.266(7)-2.297(5) A, and the P-S distances are between 2.044(10)
and 2.059(6) A.
Gallium Halides.-GaF3,3H,0 may be prepared in 93-96% yield by dissolving Ga in a mixture of 40% HF and 30% H202.582
Mass spectrometric
have been used to determine the
vapour pressures of GaF, and (GaF,),. Calculations of the enthalpies and
entropies of sublimation gave the following results: GaF3 (298 IS) 58.8 If:
3 kcal mol-l, 44.6 f 3 e.u., respectively, and (GaF,), (914 K) 71.0 f
4 kcal mol-l, 42.8 e.u., respectively.
Chemical analysis and i.r. spectra of the hydrolysis products of the ammine
adducts of GaF3,3NH, and InF3,3NH, show that they are ammonium dihydroxotrifluoro-gallateand -indate, respectively, and not hydrated ammines
of the corresponding fluorides.584
581
582
583
684
P. Buck and C. D. Carpentier, Acta Cryst., 1973, B29, 1864.

G. E. Revzin and L. M. Petrova, Metody. Poluch. Khim. Reaktiv. Prep., 1972, 24, 79.
D. H. Feather, A. Buchler, and A. W. Searcy, High Temperature Sci., 1972, 4, 290.
S. P. Kozerenko, S. A. Polishchuk, and N. 1. Sigula, Russ. J. Inorg. Chem., 1972, 17,
984.
205
Using previously published vibrational data, values of force constants,
Coriolis coupling constants, and mean amplitudes of vibration at 0, 298.16,
and 500 K have been calculated for GaF:-.5s5 An independent report586of
a force-constant calculation on GaF:-, together with FeFi- and ScFi-, using
a generalized valence force field (GVFF) and a modified Urey-Bradley
force field (UBFF) has been published.
The rate parameters for exchange of Cl- with GaCl; in concentrated
aqueous HCl have been obtained by 35Cln.m.r.; the enthalpy and entropy
of activation were calculated (A$ = 30.1 f 1.5 kJ mol-l; A S = -24 f 6
J mo1-1 K-1 587
>.
Crystals of (Me4N),Ga,CI, are cubic (space group Pa3; a = 13.097 A),
and the anion possesses D3a sym~netry.~*~
r(GaGa) is 2.390(12) A, r(CaC1) is
2.296(4) A, LGaGaCl is 113.9(1)*, and LClGaCl is 104.6(1)". These results
confirm the presence of GaII in the anion.
Vibrational spectra and assignments have been reported for Ga2Xi(X = C1, Br, or I) as NMer salts. A normal-co-ordinate analysis was performed on the Ga,CI:- ion which indicated a value for the Ga-Ga stretching
force constant of 217 N m-l. This is significantly higher than other reported
M-M stretching force constants, e.g. in Ge,H6, the Ge-Ge stretching force
constant is 160 N m-1.589
A partial assignment has been proposed for the i.r. absorptions of mixed
gallium halide complexes [GaX3Y]- (X, Y = C1, Br, or I); see Table 2.590
Table 2 Vibrational assignments in GaX3Y- complexes. (All figures in cm-l)

v(GaY)
v(GaX3)
r
Complex
A1
A1
GaC1,BrGaCl,IGaBr,ClGaBr,IGa1,ClGa1,Br-
3 70
368
274
273
225
254
352
345
241
25 1
194
221
278, 259
208, 215
3 60
226
363, 355
270
Deformation modes and lattice vibrations could not be distinguished.

The following calculated thermodynamic parameters have been proposed
for Ga,CI,:591 AG&* = -256.5 f 5 kcal mol-l; AH,.,, = -292.5 f 2.5
kcal mol-l; S,,, = 92.5 =t: 5J mol-l K-l.
590
B. B. Srivastava, A. K. Dublish, and A. N. Pandhey, J. Mol. Structure, 1973,15,421.

N. K. Sanyal and L. Dixit, Spectroscopy Letters, 1973, 6 , 49.
S. F. Lincoln, A. Sandercock, and D. R. Stranks, J.C.S. Chem. Comm., 1972, 1069.
K. L. Brown and D. Hall, J.C.S. Dalton, 1973, 1843.
C. A. Evans, K. H. Tan, S. R. Tapper, and M. J. Taylor, J.C.S. Dalton, 1973, 988.
A. N. Grigor'ev, A. I. Grigor'ev, L. M. Mikheeva, and I. B. Baranovskii, Russ. J .
591
Inorg. Chem., 1972, 17, 1695.

P. P. Fedorov and P. I. Fedorov, Russ. J . Inorg. Chem.. 1972, 17, 457.
585
586
687
588
589
206
The magnitude of the heat of solution of GaCI, in benzene has been used592
to estimate theheat of formation of thecomplex GaCl,,C,H,as 11.3 kcalmol-l.
The value for the analogous mesitylene complex is 15.2 kcal mol-l.
The anomalous behavior of anionic complexes of the type MX, (M =
GayTI, Fe, or Au; X = C1, Br, or I) on cation-exchange columns has been
investigated.593
A crystalline complex of GalI1 chloride with 1 -piperidinoanthraquinone
has been isolated.5941.r. and electronicspectra are consistent with the formulation (116).
The Ga-GaBr, and KBr-GaBr, systems have been studied by d.t.a. The
former gives evidence of 3 compounds, GaBr, Ga[GaBr,], and Ga[Ga,Br,].
The latter gives only KGaBr, and
Solid-phase vibrational spectra of Ga,Br; were not able to distinguish
between CZ,or C,symmetry. Assignments proposed were based on those for
C1207 and the following values for the bridge stretches were given:
v,(GaBrGa) 195 cm-l ;v,,(GaBrGa) 222
This suggested the following
reassignment for the analogous modes in Ga,CI; : v,(GaClGa) 276 cm-';
v,,(GaClGa) 286 cm-l.
The Raman spectra of the gallium iodides Ga,I,, Ga2T3,and GaJ, show
that these are, respectively, Ga+[Ga14]-, Gai+[Ga216]2-,and Ga214,Ga416.597
Other Gallinm Compounds.-Phase diagrams of the systems M,Se3-Ga,Se3,
(M = La, Nd, Gd, or Y ) have been obtained.598Two types of intermediate
phases were observed: M6Ga1,-,&14
(hexagonal, M = La-Gd)
and
MGaSe, (orthorhombic, M = Gd-Dy).
593
594
59s
596
597
I. P. Romm, E. N. Kharlamova, and E. N. Gur'yanova, J. Gen. Chem., (U.S.S.R.),

1972,42,2246.
G. Pfrepper, 2.Chem., 1973, 13, 67.
B. E. Zaitsev, N. P. Vasil'eva, B. N. Ivanov-Emin, and M. V. Gorelik, Russ. J . Inorg.
Chem., 1972, 17,200.
D. Mascherpa-Corral and A. Potier, Bull. SOC.chim. France, 1973, 1912.
A. Grodzicki and A. Potier, J. Inorg. Nuclear Chem., 1973, 35, 61.
L. G. Waterworth and I. J. Worrall, J . Inorg. Nuclear Chem., 1973,35, 1535.
A. M. Lozach and M. Guittard, Bull. SOC.chim. France, 1973, 6 .

207
If a mixture of Rb or Cs and Ga in a rotating autoclave is heated to
200 OC for 24 h with 200 atm H, (Rb) or 300 atm H, (Cs), the gallohydrides
RbGaH, or CsGaH, are produced directly and in good yield.599
A study of the Ga-Mg phase diagram has confirmed the existence of the
compound Mg,Ga,.600
The Mo-Ga system has been studied by thermal analysis, X-ray diffraction, electron microprobe, and metallography.601Two intermetallic compounds were identified and characterized as follows : (a)Mo3Ga, peritectic
(1820 f 20 "C), (b) MoGa5, peritectic (835 & 5 "C).
The phase diagram of Cu,Te-Ga,Te, has been determined.602A compound Cu,Ga,Te, is formed which is a defect sphalerite-type semiconductor
(energy gap 1.08 f 0.05 eV).
The U-Ga system has been studied by X-ray diffraction, metallography,
and thermoanalysis over a wide concentration range.603A phase diagram was
constructed and 3 compounds were detected and characterized, namely
U,Ga,,UGa,,and UGa,.
Thermodynamic functions have been calculated for liquid binary Ga-Pb
alloys in the composition range 10-90 atom % Pb. Enthalpies and excess
entropies of mixing at 1000 K were reported.604
4 Indium
General and Analytical.-An analytical method for the rapid and carrier-free
separation of "l1n (half life 2.81 d), prepared via 109Ag(4He,2n)1111nor
lloCd(d,n)lllIn, is based on the fact that indium, in the presence of excess
Agl or CdII, is preferentially extracted from aqueous solutions into nheptane solutions of bis(2-ethylhexyl) hydrogen phosphate (Ag and Cd
remain in the aqueous phase). The InIlI can then be stripped from the
solvent phase with HCI. The separation time is < I 0 mh605
The direct determination of the limiting conductance of the &In3+ion is
not possible because of hydrolysis. An indirect estimate of 56.3 0-l is
probably too high.606
Liquid ion-exchange and tracer (l141n) studies have been made of the
hydrolysis of In111 in acidic solution.607
A spectrophotometric determination of indium has been reported, using
Xylenol Orange, after extraction of the metal into an organic phase using a
long-chain primary amine.608
599
601
604
603
604
606
607
608
L. I. Zakharkin, Synth. Inorg. Metal-org. Chem., 1972, 2, 311.

W. Stahlin, J . Less-Common Metals, 1973, 32, 395.
J. D. Barnaud, R. E. Siemens, and L. L. Oden, J . Less-Common Metals, 1973,30,205.
A. Congiu, L. Carbato, and P. Manca, Materials Res. Bull., 1973, 8, 293.
K. H. J. Buschow, J. Less-Common Metals, 1973, 31, 165.
A. F. Kwang and Z. A. Munir, J. Less-Common Metals, 1973, 30, 387.
R. A. Wood, S. T. Wakakuwa, and N. S. Macdonald, J. Inorg. Nuclear Chem., 1972,
34, 3517.
A. N. Campbell, Canad. J. Chem., 1973, 51, 3006.
S. LBsztity, Radiochem. Radioanalyt. Letters, 1972, 12, 27.
K. Akatsuka, Japan Analyst, 1972,21, 1372.
208
The extraction behaviour of InlI1 into CHCI, solutions containing both

N-benzoyl-N-phenylhydroxylamine(HB) and thenoyltrifluoroacetone (HA)
can be accounted for quantitatively in terms of the extraction constants for
InA, and InB,, and the statistically calculated values for InAzBand I~IAB,.~~
Complex formation in the aqueous systems InIII- or TIIII-Methylthymol Bluediphenylguanidine has been studied.610The resulting complexes
may be quantitatively extracted into a mixture of chloroform and isopropyl alcohol.
The extraction of small amounts of Zn, TeIV, T P , Ag, SnIV, Co, Bi, Sc,
SbIII, Hg, and Cd together with In111 from HBr solutions is greatly reduced
by the use of tributyl phosphate as extractant.611
A study of the adsorption characteristics of l13SnIV and 113mXnIIIon
silica gel, alumina, and Dowex I from an aqueous HCl medium has been
carried out, in order to deduce the optimum separation conditions!12
Compounds containing In--8, In-S, and Pn-Se Bonds.-A
number of
compounds derived from In111 acetate have been studied by Habeeb and
Among these was indium diacetate, produced by the electrolysis of
In in acetic acid. This has a lattice of In(OAc), In(OAc), containing
polymeric carboxylate-bridged units [similar to In (OAc),, (Me4N),In(OAc)S
(C10J3, etc.], which is unrelated to the indium dihalides.
Acetato(dimethyl)indium(m) crystallizes in the orthorhombic space group
Pnma [a = 7.265(2), b = 7.325(2), c = 13.286(5)A; Z = 41. The In is
six-co-ordinate, as shown in (117) (bond length/&, i.e. the InC,02 unit is
approximately tetrahedral, with two further 0s from bridging acetates at
2.60 A.614
120
3.60
(117)
In(OH)CO, is prepared in 97% yield by the reaction of InCI, with 5 %

NaHCO, solution.615
The reaction of Inrr1 chloride with Rb or NH, tripolyphosphates has been
studied by solubility and pH measurements. Basic indium tripolyphosphates
of variablecompositionand the mixed tripolyphosphates MIn,(P,Olo),, 10H20
6oD
H. J. Le Roux and K. F. Fouche, J. Inorg. Nuclear Chem., 1973, 35, 2017.

M. K. Akhmedi, E. L. Glushchenko, and E. L. Gasanova, Russ. J. Inorg. Chem., 1972,
611
612
A. B. Sokolov and Yu. A. Zolotov, Russ. J. Inorg. Chem., 1972, 17, 584.
M. El-Garhy, T. Palma, and E. Lorca, J. Inorg. Nuclear Chem., 1973, 35, 1703.
J. J. Habeeb and D. G. Tuck, J.C.S. Dalton, 1973, 243.
F. W. B. Einstein, M. M. Gilbert, and D. G. Tuck, J.C.S. Drrlton, 1973, 248.
G . E. Revzin, Metody Poluch. Khim. Reaktiv. Prep., 1972,24, 37.
17, 646.
613
614
615

209
were isolated.616The indium tripolyphosphate In,(P3010),,21H20 is obtained
from the InC13-Li,P3010-H20 system at 25 0C.617The anhydrous analogue
cannot be prepared by thermal dehydration, since this leads to breakdown
of the structure of the tripolyphosphate as well as H 2 0 loss.
The instability constant of the complex InSOi has been found (using the
inhibition by SO:- ions of the catalytic polarographic current in the Ins+-Iand In3+-NCS- systems) to be Kl = 1.0-1.1 x lo-, [at an ionic strength
(I)of 1.1 at 25 0C].618
The nuclear quadrupole coupling of l151n in NH41n(S04),,12H20 (ammonium indium alum) is found to change sign with changing temperature,
from f4.1 MHz at 265 K to ~ 3 . MHz
8
at 138 K.619Attempts to obtain
n.m.r. signals below the ferroelectric phase transition (To= 127 K) were
unsuccessful.
In,(Se04),,9H,0may be prepared by dissolving freshly precipitated In(OH),
in dilute H,Se04. Thermographic study shows successive loss of H 2 0 molecules, with partial reduction to SeIV at ca. 325 "Cand extensive decomposition
at 55OoC (giving In203).620The i.r. spectrum of this compound was also
reported. The In,(SeO4),-H2SeO4-H20 system has been studied621by the
isothermal solubility method at 20C. The formation of the compounds
In,(SeO,), ,8H20, In, (SeO4),,H,SeO4,9H20, and In2(SeO4),,2H2SeO4,9H2O
was established.
Indium(m) chloride and K,Cr04 react in aqueous solution to give a
sparingly soluble basic indium dichromate In(OH)Cr04,61n(OH),.622This
was characterized by X-ray powder diffraction and i.r. spectra; the latter
showed characteristic absorptions of co-ordinated CrO, and OH groups.
Double molybdates and tungstates of Rb with In, RbIn(Mo04), and
RbIn(WO,),, together with KIn(WO,),, have been prepared by crystallization from solution in a melt.823Single crystals of NaIn(MoO,), have also been
obtained.624They melt (with some decomposition) at 785 "C, and belong
to the triclinic space group PI (a = 7.18, b = 7.18, c = 14.90A; a = 92',
/3 = 88", y = 82"; 2 = 4). The In atoms are six-co-ordinate, in a distorted
octahedral arrangement, by oxygen atoms [r(InO) lies in the range 2.062.27&. Another group of Russian workers have studied the crystal
616
617
618
OIQ
620
6a1
622
623
624
G. V. Rodicheva, E. N. Deichman, I. V. Tananaev, and V . V . Klimov, Russ. J. Inorg.

Chem., 1972, 17, 202.
G. V. Rodicheva, E. N. Deichman, I. V. Tananaev, and V . V . Klimov, Russ. J. Inorg.
Chern., 1972, 17, 1199.
Ya. I. Tur'yan and N. K. Strizhov, Russ. J. h o r g . Chem., 1972, 17, 1066.
W. C . Bailey and H. S . Story, J. Chern. Phys., 1973, 58, 1255.
E. N. Deichman, I. V. Tananaev, and N. V . Kadoshnikova, Russ. J. Inorg. Chem.,
1972,17, 16.
E. N. Deichman, I. V. Tananaev, and N. V . Kadoshnikova, R u m J. Inorg. Chem.,
1972, 17, 117.
B. N. Ivanov-Emin, N. I. Ushakova, V. I. Kuznetsov, and B. E. Zaitsev, Russ. J.
Inorg. C h m . , 1972, 17, 1197.
P. V. Klevtsov, R. F. Klevtsova, and A. V. Demenev, Soviet Phys. Cryst., 1972, 17,
474.
R. F. IClevtsova and P. V. Klevtsov, Soviet Phys. Cryst., 1973, 17, 843.
210
Inorganic Chemistry of the Main-group EIements

structure of the closely related NaIn(WO,),; this also forms triclinic crystals,
space group Pi (a = 5.79 f 0.02, b = 19.08 f 0.05, c = 5.10 f 0.02A;
a = p = y = go f
101.625
The crystal structures of M,In6010 and M2T1,0,, (M = Rb or Cs) have

been determined.626The anionic units are built up from linked InO, or
TlO, octahedra.
The hitherto unknown compound Ca,In206 may be prepared by heating
CaIn,O, or a mixture of 3Ca0 In203, to 2000C. The compound crystallizes in the orthorhombic system (space group PbarnlD;,, with Q =
10.908, b = 16.45, c = 3.228 A), with a partially statistical distribution of
Ca and In.627A single-crystal X-ray investigation of SrIn,O, indicated that
it possessed a similar crystal structure to Ca,In206. The space group was
Pnarn/D::, (a = 9.809, b = 11.449, c = 3.265 A).628SrIn,O,, on the other
hand, belongs to the orthorhombic space group Ibrn2(C3 with a = 6.049,
b = 15.84, c = 5.81 A, and is isostructural with Ca2FeA10,, brownmillerite.
Half of the In atoms are tetrahedrally and half octahedrally c o - ~ r d i n a t e d ? ~ ~
Cell constants have been reported630for InNb04 and InTaO,, which are
isostructural with wolframite.
Interactions in the Rb2W0,-In2(W0,), system lead to the following compounds: a- and p-Rb31n(W04)3,a-, p-, y-, and 8-RbIn(W04),. The former
are produced at 350 O C , the latter at 450 0C.631
Potentiometric studies of complex formation by Id11 with a number of
organic chelating agents reveal the following order of stability : thiolactic
acid > thioglycolic acid > lactic acid > glycolic acid > a-alanine > glycine.632
Formation constants for 1:1, 1:2, and 1:3 complexes in In111 with
ethylenebis-(3-mercaptopropionate) were determined polarographically at
3OoC (p1 = 4, /3, = 130, 8, = 8600) and at 40 "C (pl = 2, /I2 = 100,
p3 = 8500).633
The ligand-exchange reaction between InL, and excess free ligand HL
(where L = CF,COCHCOR; R = Me, Bui, Ph, 2-naphthyl or 2-thionyl)
has been studied in the solvents di-isopropyl ketone, acetonitrile, benzene,
and DMSO. Lifetimes of the reactants (from 19Fn.m.r. linewidths) show that
the exchange is first-order in [InL,] and zero-order in [HL]. Coalescence
temperatures for the collapse of the 19F n.m.r. chemical shift between free
and complexed ligand give values of AG for the exchange process (e.g. 15.1
625
626
627
6a8
629
630
631
P. M. Fedorov, V. I. Pakhomov, and V. N. Karpov, Russ. J. Znorg. Chem., 1972, 17,

462.
D. Fink and R. Hoppe, Naturwiss., 1973, 60, 430.
R. von Schenck and H. Muller-Buschbaum, 2. anorg. Chem., 1973, 398, 15.
R. von Schenck and H. Muller-Buschbaum, Z . anorg. Chem., 1973,398,24.
R. von Schenck and H. Muller-Buschbaum, 2. anorg. Chem., 1973,395,280.
J. Liebertz, Acta Cryst., 1972, B28, 3100.
S. A. Pavlova, M. V. Mokhosoev, and E. I. Get'man, Russ. J . Inorg. Chem., 1972,17,
81.
632
633
R. Sarin and K. N. Munshi, J. Inorg. Nuclear Chem., 1973, 35, 201.

R. S. Saxena and V. S. Chaturvedi, J. Znorg. Nuclear Chem., 1972,34, 3272.
21 1
kcal mol-l for R = Ph). The rate-controlling process in the exchange can be
identified as the rotation of one unidentate ligand about a partial double
bond prior to intramolecular proton transfer to a second unidentate ligand.634
Complex formation of In with ethylenediamine-NN'-dimalonic (eddma),
-disuccinic (eddsa), and -diglutaric (eddga) acids has been
Species
InL- and InHL are formed in each case, and stability constants were measured
at 25 0C?35
A study of the crystal structure of tris(pentamethy1enedithiocarbamato)indium(m), In(S,CNC,H,,)3, led to the following conclusions:636(i) the pair
of C-S p,-electrons in (118) are delocalized; (ii) the N atom n-bonds
significantly with the C of S,CN (giving a short C-N bond); (iii) the sevenatom group (118) is planar; (iv) the 3 organic rings are in the chair conformation; (v) the S-In-S
chelate angle is only 69"; and (vi) the coordination at the In atom is closer to trigonal-prismatic than to octahedral.
Complexing of In and T1 with NCS- and NCSe- has been studied polarographically.637The following logarithmic stability constants were deduced
(at 27.0 f 0.1 "C): TI(SCN) 0.63; Tl(SeCN) 0.97; Tl(SeCN); 0.88;
TI(SeCN); 1.24; In(SCN),+ 0.78; In(SCN)i 2.49; and In(SeCN),
3.91. 1.r. spectra were consistent with M-S or M-Se bonding in all
of these complexes.
pH methods have been useds3* to examine complex formation between
In3+ and thioglycolate, HOCH,CH,S-, and show that only mononuclear
species In(SR)!,%")+ (n = 1 - 4 ) are formed. In the presence of GI-, mixed
complexes In(SR),CI, (3- n- i 1+ are formed. Stability constants for the thioglycolates and mixed species were given.
Heating a stoicheiometric mixture of In, Ni, and Cr sulphides in a quartz
tube at 800 OC for 6 days produces a new spinel phase, In(NiCr)S,, which is a
semiconductor (resistivity > lo5 crn-l)?
The crystal structures of ZnIn,S, and Zn21n2S5have been determined.s40
The crystal structure of Bi,In,S,, the first compound characterized in the
634
635
636
637
638
639
640
G. T. Tanner, D. G. Tuck, and E. J. Wells, Caizad. J . Chem., 1972, 50, 3950.

I. P. Gorelov, M. Kh. Kolosova, and A. P. Samsonov, Zhur. analit. Khim., 1973, 28,
1080.
P. J. Hauser, J. Borchner, and A. F. Schreiner, Inorg. Chem., 1973, 12, 1347.
R. S. Ramakrishna and R. Thuraisangham, J. Inorg. Nuclear Chem., 1973,35, 2805.
K. Tunaboghi and G. Schwarzenbach, Helv. Chim. Acta, 1972, 55, 2065.
W. Schlein, Bol. SOC.Childna Quim., 1972, 19, 10.
F. G. Donika, S. I. Radautsan, S. A. Semiletov, G. A. Kiosse, and I. G. Mustya,
Soviet Phys. Cryst., 1972, 17, 575, 578.
15
212
pseudo-binary system In,S,-Bi,S,, has been determined. The space group is

P2,/m, having a sulphur framework, three In atoms co-ordinated octahedrally by six S stoms (2 regular, l distorted), and a fourth In atom with
distorted tetrahedral geonetry. Of the two Bi atoms, one is six-, the other
seven-~o-ordinate.~~~
The high-temperature polymorph of AgInS, is orthorhombic (a = 7.001,
b = 8.278, c = 6.69A; space group probably Pna2,), with a distorted
wurtzite structure and a phase transition at 620 f 10 OC (m.p. 880 f 10 "C).
A new cubic phase AgIn,S8 was also
A tabulation of the thermodynamic properties of In,Se in the temperature
range 273.5-2000 K has been published, together with measurements of its
saturated vapour pressure.643
Two determinations of the crystal structure of In$% have been made.644*645
Both agree on the space group (Pnnm, orthorhombic) and cell parameters
(within experimental error), but they describe the structure in different
ways. OnesP4refers to the presence of In+ ions and covalently bound groups
having the overall formula In,Se;, within which the In-In distances (2.75 tf)
are well within the expected range for direct, covalent In-In bonding. The
other645prefers a description in terms of endless interlocking chains consisting of five-membered In-Se rings, crosslinked by strongly bound InIn-In units, forming a continuous sheet, which may be regarded as containing In!+ ions.
The phase diagram of the In,S%-Sb,Te, system has been obtained; the
formation of a compound 31n2Sq,2Sb,Te, was indicated.646
Indium Halides.-The radiofrequency spectrum of 1151n19F has been unsuccessfully examined with the aim of finding an electric hexadecapole interaction of the indium nucleus (the upper limit for any such interaction was
2~HZ).~~'
InOF possesses an orthorhombic unit cell (space group Fddd; a = 8.356 f
0.005, b = 10.186 f 0.005, c = 7.039 f 0.005 A; 2 = 16).648 The In is
six-co-ordinated, in a distorted octahedral manner, by an ordered arrangement of 0 and F atoms. The In(O,F), octahedra are joined via edges and
corners, giving a loose three-dimensional network.
Pure InCl may be prepared by heating In in anhydrous HCl at 300 0C.649
641
643
e43
644
615
646
647
648
64n
G. Chapuis, C. Gnehm, and V. Kramer, Acta Cryst., 1972, B28, 3128.

R. S. Roth, H. S. Parker, and W. S. Brower, Materials Res. Bull., 1973, 8, 333.
J. H. Greenberg, V. A. Borjakova, and V. F. Shevelkov, J . Chem. Thermodynamics,
1973, 5, 233.
A. Likforman and J. Gtienne, Compt. rend., 1972, 275, C, 1097.
J. H. C. Hogg, H. H. Sutherland, and D. J. Williams, Acta Crysf., 1973, B29, 1590.
D.P. Belotskii and L. V. Legeta, Itzoug. Materials, 1972, 8 , 1677.
R. W. Hammerle, R. van Ausdal, and J. C . Zorn, J. Chem. Phys., 1972, 57,4068.
M. Vlasse, J.-C. Massies, and I3. L. Chamberland, Acfa Cryst., 1973, 329, 627.
L. F. Bereslovtseva and V. I. Shereshkova, Tr. Severokavkaz. Gernomet. Inst., 1970,
55.
Elements of Group I I i
213
The molecular absorption spectrum of InCl has been observed in a flame,
in the region of 2670 A.650This characteristic spectrum is also seen661when a
solution of In in aqueous HCIO, is aspirated into an air-acetylene flame.
This indicates that a recombination reaction between indium and chlorine
occurs in the flame, following the thermal decomposition of HCIO,.
The He I photoelectron spectra of InX (X = C1, Br, or I) have been reported.652These data, together with earlier work on other Group I11 monohalides, ab initiu calculations on BF, AlCI, and GaCl, and semi-empirical
calculations on the others, have enabled a general description of bonding
in such systems to be given. An MO localized on the electronegative atom
is classified as bonding whereas one localized on the positive ion has antibonding character. Such a description is quite different from that appropriate for covalently bound molecules.
A study of the composition of the vapour of the indium chlorides In,CI,,
In,CI,,,,, and In,CI,, has been made using positive- and negative-ion mass
spectrometry. Thus InnC13n,2was shown to contain the molecules InCl,
InCI,, In2C12,and In3C13.653
Interactions in the PbClz 21n 42InCl Pb and 21nC1,
3Zn
3ZnC1, 21n ternary reciprocal displacement systems have been investigated
by d.t.a.654*655
The gas-phase structure of the thallium(1) tetrachloroindate molecule as
determined by electron-diffraction data is analogous to those of NaAlF, and
KAlCl,. The InCl, fragment is tetrahedral [r(InCl) 2.37(1) A] and the unit
(1 19) is planar. r(TlC1) is 2.91 (2) A and LClTlCl is 83.656
TI
7\
l151n chemical shifts in n.m.r. spectra of In-halogen complexes have been

measured in solution.657They fall in the following sequence: InCI; <
InBr; < [In(R20)6]3+< InI;. l151n linewidths are largely determined by
quadrupole relaxation, and they may be used to study the symmetry of the
complexes. Indium, when extracted into organic solvents from aqueous HCl,
HBr, or HI solutions, exists as tetrahedral species, although the existence
650
6B1
652
653
654
655
656
657
H. Haraguchi and K. Fuwa, Chem. Letters, 1972, 913.

H. Haraguchi, M. Shiraishi, and K. Fuwa, Chem. Letters, 1973, 251.
J. Berkowitz and J. L. Dehmer, J . Chem. Phys., 1972,57, 3194.
A. S. Sultanov, Russ. J. Inorg. Chem., 1972, 17, 309.
Yu. P. Afinogenov, L. I. Shumeiko, andT. N. Larionova, Russ. J. Inorg. Chem., 1972,
17, 916.
Yu. P. Afinogenov and A. A. Anokhina, Russ. J. Inorg. Chem., 1972,17, 1463.
V. P. Spiridonov, Yu. A. Brezgin, and M. I. Shakhpironov, J. Struct. Chem., 1972, 13,
293.
H. Haraguchi, K. Fuwa, and S. Fujiwara, J. Phys. Chem., 1973, 77, 1497.
214
- -
of ion pairs H+ - InX;, (X = C1, Br, or I) is indicated by both lH and

Il5In n.m.r.
Far4.r. spectra have been reported for benzene s o h tions containing InIII
or TllI1 halides and quaternary and tertiary ammonium halides.658Spectra
consistent with the presence of both MCI, and MC1:- species were observed
in the quaternary ammonium halides, but only MX, (X = C1 or Br) were
present in the others. The symmetries of the four-co-ordinate species appeared to be either Tdor C,,,dependent upon the nature of the cation and on
the metal halide: ammonium salt ratio. The five-co-ordinate species appeared to be of D3hsymmetry.
Using previously published vibrational data, Contreras and Tuck have
calculated force constants for the In111 systems InX; (X = C1, Br, or I),
InCl:-, and InCl:-, and for the In1 complexes InXi- (X = C1, Br, or I),
(see ref. 661, below), using a simplified GQVFF model. For InIII, f(1nX)
decreases linearly with increased co-ordination number. For the isoelectronic series Inxi-, SnX;, SbX,, log[f(MX)] varies linearly with the
changing oxidation state of M.659
Force constants, Coriolis coupling constants, and mean amplitudes of
vibration of InC1;- have also been calculated from previously reported
vibrational
The stretching force constants of the isoelectronic
sequence are in the following order: InC1:- < SnClt- < SbCl;.
The halide salts of the dipositive NN-dimethyl4,4-bipyridiniumcation
react with indium monohalides to give the first reported examples of salts
containing the Inxi- anion, [Me2bipyl2+[InX,I2-(X = Cl, Br, or I). These
were characterized by elemental analysis, conductivity measurements, and
vibrational spectroscopy. The last technique revealed that the anions possessed C,,symmetry, e.g. for InCli-, v1 252, v2 102, v3 185, and vq 97 cm-l.
Reactions of the same cation with InX, produced [Me,bipy]InCl, or [Me,bipy][InX,]X (X = Br or I). The InC1:- ion has C,, symmetry. In11 halides
reacted to give a mixture of the In1 and In111 anions.661
Mass-spectrometric evidence has been obtained for the existence of the
following gas-phase systems: InUCl,, In2UCl,,, BeInCl,, BeIn2C1,, Be21nC1,,
Be,InCl,, ZnInC15, SnInCl,, TlPbCl,, TlCdCl,, Tl,ThCIG, TlUCl,, TlU2C19,
and T12UC16.662
A new indium subhalide, of composition InBrl.28, is formed as an intermediate in the oxidation of InBr by alkyl bromides.663This composition
corresponds to In7Br9, and it is tentatively formulated as 6In+(InBr:-).
3Br-, since a Raman band at 163cm-l is observed, characteristic of
InBr:-.
658
659
660
661
662
663
R.A. Work tert. and M. L. Good, Spectrochim. Acta, 1973, 29A, 1535.
J. G . Contreras and D. G . Tuck, Znorg. Chem., 1972, 11, 2967.
A. K. Dublish and D. K. Sharma, Spectroscopy Letters, 1972, 5 , 387.
J. G . Contreras, J. S. Poland, and D. G. Tuck, J.C.S. Dalton, 1973, 922.
M. Binnewies and H. Schafer, Z . anorg. Chem., 1973, 395, 77.
L. G . Waterworth and I. J. Worrall, Znorg. Nuclear Chem. Letters, 1973, 9, 237
Elements of Group I I l
215
An 81Br n.q.r. examination of InBr, shows that there are at least two
solid modifications of this compound.664
The following phase diagrams have been reported for the binary systems:
InBr,-LiBr (the compound Li,InBr, is formed) ; InBr,-KBr (K,InBr,) ;
InBr,-NH,Br [NH41nBr4,(NH4)31nBr6],665
and also InI-MI (M = Na, K,
Rb, or Cs); and 1n12-M1 (M = Nay K, or CS).,,~
A rapid and convenient synthesis of InI, has been described.667If dry
diethyl ether is condensed on to a stoicheiometric mixture of In and I, in
vacuo and the mixture is shaken, a clear solution results. After ca. 30 minutes
a white crystalline deposit of InI,,Et,O is produced, from which InI, itself
may be obtained by pumping at reduced pressure.
The yellow form of I d , , if allowed to stand for several days in the presence
of n-butyl iodide at -20 C, is completely converted into the previously illcharacterized red isomer.668The Raman spectra of the two forms show that
they are structurally dissimilar, the yellow form being formulated as h216
(having bridged, tetrahedral co-ordination at In). The red form, In13, is
polymeric, with octahedral co-ordination at In.
Other Indium Compounds,-Anionic thiocyanato-complexes of In111 have
been prepared-with Ph,As+ or (Ph,PCH,Ph)+ as cation the anion is
[In(NCS)5]2-, while with Me4N+, Et,NH+, and BuYN+, [In(NCS)6]3- is
present. Vibrational spectra are consistent with N-bonding of the ligand in
each case, in agreement with earlier work on neutral adducts of Inrr1 thio~yanate.~~~
Apparent stability constants for InIr* thiocyanato-complexes have been
shown to include stability constants of hydroxo- and mixed thiocyanatohydroxo-indium(u1)complexes. The stability constant of the 1:1 thiocyanatocomplex is only truly constant at pH ca. l.,
The formation constants of indium(m)-l ,lo-phenaiithroline and -2,2bipyridyl complexes have been determined, as follows: (1 ,lo-phen) B1
5.0 x lo5, B2 1.1 x 1O1O, B3 1.0 x 1014;(bipy) & 5.6 x lo4, p2 1.0 x 108.671
In[Co(CO),], crystallizes in the monoclinic space group P2,/n [a =
= 113.91(4); 2 = 41. Dis18.834(8), b = 6.806(3), c = 16.606(7)A;
crete molecules are present, having approximate c,, symmetry, and there is
an average In-Co bond length of 2.594(3) A. The latter is not consistent
with In-Co p,-d,, bonding.672
664
665
666
667
669
670
671
67a
T. Okuda, Y. Furukawa, H. Shigemoto, and H. Negita, Bull. Chem. SOC.Japan, 1973,

46, 741.
A. G. Dudoreva, K. Gladis, P. I. Fedorov, A. I. Ezhov, and V. M. Akimov, Russ. J .
Znorg. Chem., 1973, 18, 109.
P. I. Fedorov, N . S. Malova, and V. A. Zukharev, Russ. J. Inorg. Chem., 1972,17,286.
M. J. S. Gynane, M. Wilkinson, and I. J. Worrall, Inorg. Nuclear Chem. Letters, 1973,
9, 765.
M. J. S. Gynane and I. J. Worrall, Inorg. Nuclear Chem. Letters, 1973, 9, 903.
J. J. Habeeb and D. G. Tuck, J.C.S. Dalton, 1973, 96.
S. Lhsztity, Radiochem. Radioanalyt. Letters, 1972, 12, 33.
F. Ya. Kulba, Yu. A. Makashev, and N. I. Fedyaev, Russ. J. Inorg. Chem., 1972, 17,
188.
W. R. Robinson and D. P. Schussler, Inorg. Chem., 1973, 12, 848.

InTeCl is monoclinic, space group P2,lc (a = 7.42, b = 14.06, c =
7.07 A; ,B = 92.1'; 2 = 8). The compound represents a new ternary defect
tetrahedral type, in which distorted InTqCl tetrahedra form layer complexes
situated parallel to the (100) plane by sharing corners and edges which are
occupied by Te atoms. The C1 atoms do not contribute to the bonding. The
Te atoms are surrounded by three In atoms in an approximately trigonalpyramidal arrangement .673
The heats of formation of several Hg-In phases have been determined at
81 K, uiz. Hg,,In,,, Hg61n, Hg51n, HgIn, and H ~ I I I , . ~ ~ *
The InSb-AuIn section of the In-Au-Sb ternary system has been exnot~quasi-binary;
~
solid soluamined by d.t.a., X-ray diffraction, e t ~It .is ~
tions based on InSb, AuIn,, and AuIn are present.
21 6
5 Thallium
General and Analytical.-Thallium(1) may be extracted quantitatively from

1-2M-NaOH solution into CHCI, as its complex with thionalide, thioglycol-p-naphthylamide (120). The extraction is selective in the presence of
NHCOCHZSH
(120)
Na,edta and KCN, and the technique was illustrated by the determination
of trace amounts of TI from a number of standard
A new photometric method for the determination of TI in Pb alloys is
based upon the selective extraction by benzene of TI3+ ions as the triphenyltetrazolium complex. No interference from SbV, AsV, SnIV, B P I , CoII,
TeIV, GaIII, or InIII was noted, but Ad1* did interfere with the determinat ion.677
Thallium(1) can be separated from large amounts of alkali metals, alkalineearth metals, lanthanide metals, CrIII, Al, Ga, TiIV, Zr, MnII, Zn, Ni,
SbIII, Ag, FeII, HgII, or AsIII by extraction with di-Zethylhexylphosphoric
acid and back-extraction with 9M-HN03.678
Thallium may be determined spectrophotometrically in the organic
phase after extraction with di-2-ethylhexylphosphoric acid.679Tl1I1 may
therefore be estimated in solutions containing relatively large amounts of
Cd, Cu, Mg, Ni, CoyAl, Cr, Mn, Fe, Ga, Bi, In, Sb, As, or Hg.
673
674
675
676
677
678
679
G. ROOS,
G. Eulenberger, and H. Hahn, Z . anorg. Chem., 1973,396, 284.
H. P. Singh and S. Misra, J. Less-Common Metals, 1973, 32, 227.
A. A. Babitsyna and N. P. Luzhnaya, Rum. J. Inorg. Chem., 1972, 17,902.
R. A. Nadkarni and B. C. Haldar, Radiochem. Radioanalyt. Letters, 1972, 11, 367.
A. Alexandrov and A. Dimitrov, Mikrochim. Acta, 1972, 680.
V. I. Varentsova, T. F. Rodina, and I. S. Levin, Zhur. analit. Khim., 1973, 28, 1086.
T. F. Rodina, V. S. Kolomiichuk, and I. S. Levin, Zhur. analit. Khim., 1973,28, 1090.
21 7
Thallium(r1r) Compounds.-The kinetics of the isotope exchange by electron

transfer between TI1 and TllI1 {as [ T l ( b i p ~ ) ~or
]~+
[Tl(~hen)~]~+}
have been
studied using labelled 204Tl+.680
The electrode potentials of thallium couples have been measured in
fused LiCl-KCl eutectic at 450 'C. The standard molar electrode potential
I TI1 is +0.155 V (with respect to the standard Pt reference electrode),
while the TlIII I T1 couple was calculated to have a standard potential of
-0.385 V.681
Least-squares analysis of the homogeneous pyrolysis of TIM%, via the
step:
TlMe,
+=
TIMe,
+ Me
gives the expression for the first-order rate-constant, logk, = 15.10 (36400 f 600)/2.3RT. The observed activation. energy of this process
(36.4 kcal mol-l) is a reasonable measure of D(Me,T1-Me).682
Tris-(cyclopentadieny1)- and -(indenyl)-thallium(r1I) may be prepared thus :
[(p~H)a]~+TlCl~- 3C5H,Na+ -+ (C5H5),Ti
+ 3NaC1 + 2pyHCl
(and likewise for the C,H; derivative). Some i.r. bands were quoted.6s3
The crystal and molecular structures of tris(cyclopentadienyltricarbony1molybdenum)thallium(III) T1[Mo(CO),Cp], have been determined.684The
co-ordination at the TI is trigonal-pyramidal, with an average M-Mo
bond distance of 2.965 A, and an average MoTlMo angle of 119.7'. The TI
is 0.586(1) A out of the plane of the three molybdenum atoms. The crystal was
triclinic, space group PI (C,'), with a = 11.131(9), b = 17.305(16), c =
6.833(9) A;a = 98.59(5)", /I= 96.45(5)", y = 79.51(5)"; Z = 2; R factor =
0.030.
The rate of the reaction between TlIII and SblI1 in aqueous perchloric acid
is measurable by conventional methods at 60 0C.685Two transition states were
suggested, [TIOH,HSbO2I2+and [T1HSbO2I3f, reaction occurring mainly
(85 %) via the former. The rate law is tentatively:
-d [SbOf]
dt
[TP+][SbO+] kaklk2
([H+]
k,)
4- k'ka)
(m
where k, and k2 are hydrolytic constants. k3k, and kikz were measured as
2.66, 0.30 s-l at 60 "C, with overall energy and entropy of activation 16.0 f
0.4 kcal mol-l and - 13.1 f 1.8 K-l cal mol-l.
In a study of the problems arising in the analysis of the H202-T1111system,
new induced reactions were detected involving the one-electron oxidation (by
CeIV or MnO;) or reduction (by FeII) of the system.686
rise
88L
682
683
684
885
686
A. Cecal and I. A. Schneider, Radiochem. Radioanalyt. Letters, 1972, 12, 39.

J. M. Shafir and J. A. Plambeck, Canad. J . Chem., 1973, 51, 1693.
S. J. Price, J. P. Richard, R. C. Rumfeldt, and M. G. Jacko, Canad. J. Chem., 1973,
51, 1397.
N. Kumar, B. L. Kalsotra, and R. K. Multani, J . Inorg. Nuclear Chem., 1973,35,3019.
J. Rajaram and J. A. Ibers, Inorg. Chem., 1973, 12, 1313.
P. D. Sharma and Y. K. Gupta, J.C.S. Dalton, 1973, 789.
L. J. Cshnyi, F. Cseh, Z. Szil, and Z. Boti, Acta Chirn. Acad. Sci. Hung., 1972, 75, 1.
218
Thallium oxyfluoride TlOF crystallizes in the cubic space group I33m

(a = 10.78 f 0.01 A).687The structure is related to that of fluorite, but with
the TI atoms in a distorted eight-fold co-ordination.
TIF, is isostructural with P-BiF,, YF,, and a number of rare-earth trifluorides, having an orthorhombic unit cell, space group Pnma (DAB),with
a = 5.825, b = 7.024, c = 4.851 A; 2 = 4. The TI atoms can be regarded
as eight-co-ordinate: 6 fluorines describe a distorted trigonal prism about
each TI (one at 2.09, two at 2.22, two at 2.23, and one at 2.24&, with two
additional fluorines placed (at 2.49 A) outside two of the faces of the prism.688
trans- [CoCl,(en),] [TlCI,] crystallizes in the monoclinic space group
= 90.0"; 2 = 2).689 The
P2Jm (a = 6.431, b = 19.11, c = 6.472A;
TlCl, ions have C, point symmetry, being distorted tetrahedra, with r(T1CI)
between 2.412 and 2.423 A.
White, crystalline (pyH),TICl, is prepared690by the reaction of Tl,O, and
anhydrous HCl, followed by addition of pyridine and more HCI.
The kinetics of the electron-transfer process between [HTIBr,],(py) and
TI1 have been reported (py = pyridine, a-picoline, 2,4-lutidine, collidine,
or q ~ i n o l i n e ) . ~ ~ ~
The hydrolysis of TllI1 perchlorate has been investigated spectrophotometrically in H,O-dioxan (ionic strength 1.O) and H,O-DMSO (ionic
strength 3.0). The first overall hydrolysis constants are 0.3 f 0.1 in 70%
water-30% dioxan and 0.25 f 0.06 in 0.5, 1.0mol1-1 aqueous solutions
ofDMS0.692
Heats of hydrolysis of TlIII perchlorates and heats of formation of hydroxocomplexes of TI1 have been measured by direct means at 25 0C.693Enthalpy,
free energy, and entropy data relating to these systems were tabulated.
Thallium(m) orthovanadate has been prepared by the reaction of Tl,O,
V,O, in the presence of H,O. This species has never before been reported, and
it was characterized by its chemical reactions and its thermal behaviour,
decomposing above 300 O C , thus:
TWO,
---f
TWO,
+ go,
Its X-ray diffraction powder diagram was reported, but not indexed.694
An examination of the (NH4)2S04-TI,(S04), system has revealed the
existence of the compounds NH4T1111(S0,), and (NH4)3T1111(S0,),. The
689
690
691
693
M. Vlasse, J. Grannec, and J. Portier, Acta Cryst., 1972, B28, 3426.

C. Hebecker, 2. anorg. Chem., 1972, 393, 223.
K. Brodersen, J. Rath, and G. Thiele, 2. anorg. Clzern., 1972, 394, 13.
N. Kumar, B. L. Kalsotra, and R. K. Multani, Current Sci.,1972, 41, 785.
A. Cecal and I. A. Schneider, J. Inorg. Nuclear Chem., 1973, 35, 1565.
F. Ya. Kul'ba, E. A. Kopylov, Yu. B. Yakovlev, and E. G. Kolerova, R i m . J. Inorg.
Chem., 1972,17, 1364.
F. Ya. Kul'ba, E. A. Kopylov, and Yu. B. Yakovlev, Russ. J. Inorg. Chem., 1973, 18,
38.
M. Touboul and C. Cuche, Compt. rend., 1973, 276, C, 1191.
219
latter exists in two forms, of which the high-temperature variety has rhombohedral symmetry (a = 15.64 f 0.03, c = 9.21 f 0.02 A). Its thermal decomposition was studied, and one of the products isolated was TI~H(S0,)2.6s5
T13+ reacts with 2-thenoyltrifluoroacetone (HL) in a M-HN0,-EtOH
mixture to give TILT, which was studied p h o t ~ m e t r i c a l l y . ~ ~ ~
Anhydrous liquid compounds HT1C14,2L [L = (BuO),P, (BuO),BuPO,
(BuO)Bu,PO, or Bu3PO]have been prepared and their i.r. spectra recorded.
Characteristic bands due to the 0 - - H bond in [H,2L]+ were seen in the
region 1300-1 600 ~ m - ~ . ~ ~ ~
Stability constants of the normal and monoprotonated TlIII complexes
of ethylenediamine-NN'-disuccinic, -dimalonic, and -diglutaric acids have
been determined at 25 "C and an ionic strength of 0.1 by a potentiometric
technique, using a Pt electrode. The stability of these complexes decreases
along the series as written because of decreasing basicity of the electrondonating nitrogen atom in the ligand molecule.698
Sr,Tl,O, has been prepared for the first time, from an appropriate mixture
of the oxides.699It crystallizes in the tetragonal space group P4,nm (Ci,)
(a = 5.006, c = 18.73 A). Sr2+ has trigonal-prismatic co-ordination, while
the TP+ has two nearest oxygen-neighbours (2.08 A) with two at 2.50 A.
It has been shown that the thallium ions in non-stoicheiometric pyrochlores T11+a(Tal+aw1-a)06occupy two different types of position, the ratio
depending upon the value of a.700
Thallium(1) Compounds.-A comprehensive review of TI' chemistry has been
published by Lee.701
The bonding of TI+ ions in the zeolite lat tice has been investigated by broadline 205T1n.m.r. spectroscopy.702
Measurements of the low-frequency Raman spectrum of TlN, at various
temperatures are consistent with the existence of a low-temperature phase
transition, involving distortion of the N; ion, at 225 K.703
Salicylato-(1,lo-phenanthroline)thallium(I) exists in dimeric form with
five-co-ordinate T1. The phenanthroline is bidentate, with T1-N distances
of 2.65 and 2.71 A, as is the salicylato ligand, although it is here markedly
unsymmetrical (with T1-0 distances of 2.65, 2.98 A). Further, the former
oxygen undergoes a weak 'bridging' interaction with the second TI atom of
the dimer (TI - - 0 = 3.00 A).7o4
J. Tudo and B. Jolibois, Compt. rend., 1973, 276, C, 347.

V. Z. Amarii, Pouerkh. Yavleniya Adsorbtsiya. Koord. Vzaidiodeistuie, 1972, 45.
15~' S. P. Khramenko, L. K. Chuchalin, A. 1. Rezvukhin, and Z. N. Mironova, Izvest.
sibirsk. Otdel. Akad. Nauk. S.S.S.R., Ser. khim. Nauk, 1973, 53.
6 9 8 I. P. Gorelov and M. Kh. Kolosova, Russ. J. Inorg. Chem., 1973, 18, 46.
6 9 9 R. von Schenck and H. Muller-Buschbaum, 2. anorg. Chem., 1973,396, 113.
' 0 C. Michel and B. Raveau, Materials Res. Bull., 1973, 8 , 451.
701 A. G. Lee, Coordination Chem. Rev., 1972, 8, 289.
7 0 2 D. Freude, A. Hauser, H. Pankau, and H. Schniedel, Z . phys. Chem. (Leipzig), 1972,
251, 13.
'03 Z. Iqbal and M. L. Mehrotra, J. Chem. Phys., 1972,57, 2637.
704 I. L. Hughes and M. R. Truter, J.C.S. Dalton, 1972, 2214.
695
696
220
pH-potenti~metric~~~
and p o l a r ~ g r a p h i cmethods
~~~
have been used to
determine the stability constants of the TIHL2-, TlL3- and T1,L2- complexes,
where L = ethylenediamine-NN'-dimalonic, -disuccinic, and -diglutaric
acids (eddma, eddsa, and eddga). For all three types of complex the order
of stability is L = eddma > eddsa > eddga.
Nuclear magneticrelaxation rates of 205T11in aqueous solution are markedly
dependent upon the presence of molecular oxygen, and T1-0, complex
formation has been postulated.707The rapid reversibility and reproducibility
of the relaxation data with oxygen pressure suggest that this is an ionmolecule complex.
X-Ray photoelectron spectra of a number of TI1 8-dicarbonyl compounds
have been measured, showing that the influence of substituents on the binding
energies of the T1 (4f5,2)electrons is s e c o n d - ~ r d e r . ~ ~ ~
The crystal structure of T&BO3has been determined;709the symmetry is
hexagonal, space group P63/m (a = 9.275 f 0.005, c = 3.775 f 0.002 A;
2 = 2). The unit cell contains isolated B 0 3 units, while the thallium has a
co-ordination number of 3, and its lone pair plays a significant stereochemical
role in the structure.
Mass spectral investigations on TI1 metaborate show that both TlBO, and
TI,(B02)2species are present in the gas phase.710Similarly, the mass spectrum
of the vapour above a TlF-AlF3 mixture shows the presence of TlAlF,
together with a more complex species, probably Tl2(AIF4),.
Raman spectra of solid TINO, just below its melting point and of molten
AgNO,-TINO, mixtures have been recorded.'ll 1.r. and Raman spectra of
solid TINO, (111) have been obtained and analysed in terms of the space group
( D i i ;Pbnrn) of the crystal.712
Portions of the phase diagram for the CsN02-TlN02-Ba(N0,), system
have been obtained by visual-polythermal, differential-thermal, and X-raydiffraction methods.713
205Tln.m.r. spectroscopy has been used to study the character of the Tl-0
bond in Tlf salts, especially those containing phosphate ions.714In general the
covalent character of the bond increases with T1 content, being greatest for
T13P0,.
The crystal and molecular structures of this compound have also been
determined.715The crystal is hexagonal, space group P63, with a = 8.355 f
705
'06
707
708
M. Kh. Kolosova and I. P. Gorelov, Russ. J. Inorg. Chem., 1972, 17, 953.
I. P. Gorelov and M. Kh. Kolosova, Zlzur. analit. Khim., 1973, 28, 489.
M. Bacon and L. W. Reeves, J. Amer. Chem. SOC.,1973,95, 272.
H. Kolind-Andersen, L O . Lawesson, and R. Larsson, Rec. Trau. chim., 1973, 92,
609.
70B
710
711
712
713
'14
715
R. Marchand, Y.Piffard, and M. Tournoux, Compt. rend., 1973,276, C, 177.

D. H. Feather and A, Buchler, J. Phys. Chem., 1973,77, 1599.
K. Balasubrahmanyam and G. J. Janz, J. Chem. Phys., 1972, 57,4084, 4089.
D. E. Pogarev and A. A. Shultin, Souiet Phys. Cryst., 1973, 18, 193.
P. I. Protsenko and G . F. Sh'melkova, Russ. J. Inorg. Chem., 1972, 17,452.
L. Kolditz and E. Wahner, Z . anorg. Chem., 1973, 400, 161.
M. Ganne and M. Tournow, Compt. rend., 1973,276, C, 1755.

221
0.005, c = 5.115 f 0.005 A; Z = 2. Each thallium atom lies between two
chains of tetrahedral PO, units, and has 3 nearest neighbour oxygen atoms,
one from each of 3 different PO, groups. The co-ordination is pyramidal,
with the T1 lone pair playing an important stereochemical role, as in T13B03
and T1,Si,O7.
A study of the thermal transformations of TI1 tripolyphosphate hydrate
reveals that with respect to evolution of hydrate water this compound resembles the Na+ and K+ analogues, while its tendency to degradation is more
closely similar to that of silver tripolyph~sphate.~~~
The double sulphite of TI1 and sodium, T13Na(S03),, crystallizes in the
trigonal point group P h l . The unit cell contains one molecular unit, and
a = 5.74 f 0.01, c = 7.18 f 0.01
Thallium(1) copper(I1) disulphite, TI,[CU(SO~)~],
crystallizes in the triclinic system, space group Pi [a = 5.4738(3), b = 7.3290(4), c = 5.4717(5)
A; o( = 111.638(7)', /3 = 123.570(4)', 7 = 88.019(7)'; 2 = 11. Trigonal
pyramids of SO:- and somewhat distorted CuO, octahedra (in which all of
the oxygen atoms come from different SO:- ions) are present. These form
[CU(SO,),]~- layers, which are held together by TI1 atoms. These may be
regarded as ten-co-ordinate, as shown in Figure 20, with Tl-0 distances in
the range 2.818-3.035 A, and Tl-S = 3.205
A detailed study has been made by d.t.a. of the ternary systems 2Na, 2K,
Figure 20 The environment ofthe T1 atom in Tl,[Cu(C03),]

(Reproduced by permission from Acta Chem. Scand., 1973,27,345)
717
71a
E. A. Prodan, M. M. Pavlyuchenko, L. I. Prodan, V. A. Sotnikova-Yuzlik, Yu. M.

Sotnikov-Yuzlik, and G. V. Peslyak, Inorg. Materials, 1972, 8 , 1329.
Y. Oddon, C. Caranoni, and A. Tranquard, Compt. rend., 1973, 276, C, 61.
I. Hjertbn and B. Nyberg, Acta Chem. Scand., 1973, 27, 345.
222
2T1 I( S04.719
The compounds Na2SO4,3Tl2SO,and Na2SO4,2T1,SO4,together
with some ternary compounds, were detected.
The weak Tl+ . . . ClO, complex existing in aqueous solutions has been
studied by J o h a n s ~ o n . ~ ~ ~
T12U02(C,04)2,2H20may be prepared by mixing saturated solutions of
T1I and uranyl oxalates in equimolar proportions, and evaporating at 60 'C.
The compound was characterized by d.t.a. and X-ray powder diffra~tion.'~~
TI&Ti,O, crystallizes in the monoclinic space group C2/m (a = 19.98, b =
3.776, c = 12.05 A; j3 = 106"8'; 2 = 4).722The skeletal structure results
from the association of chains of four distorted TiO, octahedra. Two adjacent octahedra share a common edge.
Three new TI1-containing phases of the quadratic oxygenated tungstenbronze type have been isolated723and characterized by X-ray powder diffraction. They are Sr2T1Nb,015,BaCaT1Nb5015,and BaSrTlNb,O,,, and all are
ferroelectric.
Two new phases have been characterized in the Tll-SnIV-O system:
Tl,SnO, crystallizes in the triclinic system, having a structure related to a
disordered-NaCl type, with missing oxygen atoms; T12Sn03is orthorhombic
(a = 12.44 f 0.05, b = 10.19 f 0.05, c = 3.24 f 0.02 A; Z = 4), possible space groups being Pbn2 or Pbnm.724
The crystal structures of j3-TIGa02, @-TlA1O2,and TlFe02 have been
determined.725All are isostructural, belonging to the space group Dgd.
T12S reacts with VS2 to give T13VS4 and VS; with NbSz and TaSz the
analogous thiometallates(v) are obtained. The metallic T1 produced gives,
with NbS, and probably with TaS2, an intercalation phase, Tl,Nb(Ta)S,.
There is no reaction between T1,S and MoS2 up to 5OO0C, and thallium(1)
thiometallates(1v) previously described could not be obtained.726
Crystalline TI1 complexes containing thiourea (tu) that have been studied
by i.r. spectroscopy include TI2C2O4,8tu,T12S20,,6tu, Tl(SCN),2tu, and
Tl,Fe(cN),,2t~.'~~
The tu (and SCN-) always co-ordinate to the TI1 via the
S atom.
The compounds Tl,M~lMIVS, (MI1 = Ni, Pd, or Pt; MIv = Pt, Zr,
Sn, or Ta) may be prepared by heating the appropriate binary sulphides in
the correct molar ratio for 2 - 4 days at 400-600 'C.X-Ray powder diffraction data were similar to those of analogous alkali-metal systems and could
be indexed on the hexagonal system.728
719
720
721
722
723
724
725
726
727
E. K. Akopov and V. G. Goryacheva, Russ. J. Inorg. Chem., 1972, 17, 1484.

L. Johansson, Acta Chem. Scand., 1973, 27, 1832.
N. C. Jayadevan, R. M. A. Dias, and D. M. Chackraburtty, J. Inprg. Nuclear Chem.,
1973,35, 1037.
A. Verbaere and M. Tournoux, Bull. SOC.
chim. France, 1973, 1237.
J. Rouex, G. Grannec, J. Portier, and P. Hagenmuller, Compt. rend., 1973,276, C , 77.
A. Verbaere, M. Dion, and M. Tournow, Compt. rend., 1973, 277, C, 371.
H. Sabrowsky, 2. Naturforsch., 1972, 27b, 1567.
V. Schmidt and W. Rudorff, 2. Naturforsch., 1973, 28b, 25.
D. M. Czakis-Sulikowska, Roczniki Chem., 1972, 46, 2315.
V. Schmidt and W. Riidorff, 2.anorg. Chem., 1973,397, 51.
223
The crystal structures of diethylthioselenophosphinatothallium(1)

[TI(Et,PSeS)] and diethyldithio- and diethyldiseleno-phosphinatothallium(1)
[Tl(Et,PX,)] (X = S or Se) have been determined.72QThe molecules form
dimers via TI$, and Tl,Se, bridging units [TI-S, TI-Se distances in the
first complex are 3.237(5) A and 3.424(4) A.] The dimers are linked via weak
intermolecular TI-Se, Tl-S bonds.
Single-crystal X-ray investigations reveal that TlGaTe,, TlInSe,, and
TlInTe, crystallize with the TlSe structure.730The TI is surrounded by 8
halogen atoms, while Ga and In are tervalent, with tetrahedral coordination.
A new series of compounds with the general formula TlIMTe, has been
characterized, where M = Y , Pr-Ln (except Eu and Yb). They crystallize
in the rhombohedra1 system, being isostructural with NaFe02.731
The new phase Ag,T1Te2 has been investigated;732the crystal is orthorhombic (space group Pmna, a = 4.60, b = 4.76, c = 15.45 A). The nearest
neighbours of T1 are four Te at 3.09 A and four Ag at 3.32 A; the co-ordination polyhedron of T1 is a cube extended along the b-axis.
The 584 A photoelectron spectra of monomeric and dimeric TlF have been
obtained. That for the monomer exhibits typical characteristics of an ionic
species, while that for the dimer is assigned in terms of a linear F-T1-TI-F
structure, having basically covalent bonding.733
Using a high-temperature microwave spectrometer capable of making
Zeeman-effect measurements in strong magnetic fields (up to 50kG), the
g factor E0.05370 (15)] and the magnetic susceptibility anisotropy [600(200)
Hz kGP2]of TlF have been determined.734
The 0, 50, 100, 200, and 250C isotherms of the ternary system H,ONH,F-TlF have been
The new ternary fluorides TIHgF, and Tl,SnF, have been prepared by
heating TlF and MF, in a gold vessel in equimolar amounts, while T12GeF,
was obtained by the reaction of Tl,CO, and GeO, in 40% aqueous H F
solution.736TlHgF, is cubic (a = 4.475 A), while the other two are trigonal
[a = 6.095, c = 4.883 8, (Sn); a = 5.887, c = 4.910 A (Ge)].
X-Ray diffraction of the YF,-TlF system, together with d.t.a., indicates
the presence of 3 phases, Tl,YF,, TlY,F, (both dimorphic, undergoing
peritectic reactions at 335 'C, 925 'C, respectively), and TlY3Fl0 (decomposing in the solid state at 825 0C).737
The solubility of TlCl in H20 and aqueous HCl (0.2-4.0mo11-1) has
J
729
730
731
732
733
734
736
736
781
S. EsperAs and S. Husebye, Actu Chem. Scand., 1973, 27, 1827.

D. Miiller, G . Eulenberger, and H. Hahn, Z. anorg. Chem., 1973,398,207.
S . KabrC, M. Julien-Pouzol, and M. Guittard, Compt. rend., 1972, 275, C , 1367.
A. S. Avilov, R. M. Imanov, and Z. G. Pinsker, Soviet Phys. Cryst., 1972, 17, 237,
J. L. Dehmer, J. Berkowitz, and L. C. Cusachs, J. Chem. Phys., 1973, 58, 1691.
R. Honerjager and R. Tischer, Z. Naturforsch., 1973, 28a, 458.
G. Coffy, Bull. SOC.chim.France, 1973, 2206.
C. Hebecker, Naturwiss., 1973, 60, 154.
J. Chassang and D. Bizot, Compt. rend., 1973, 276, C, 679.
224
been measured, and the instability constant of TlCl was found to be approx.
0.27 at the position of the solubility minimum (0.77M-HC1).738
Interactions in the ternary reciprocal displacement system :
BiCl,
+ 3Tl
--f
3T1C1
+ Bi
have been investigated by d.t.a.739

U.v.-induced darkening of TlCl crystals has been examined in an attempt
to study the processes occurring in photochromic glasses containing TlCl
part i~les.'~O
Thallium@ chloro-, thiocyanato-, and chloro(thiocyanato)-complexes
have been studied potentiometrically (using a T1 amalgam electrode) at 10,
25, 40, and 60 "C. Thermodynamic stability constants were calculated at
these temperatures. Enthalpies and entropies of formation of TlCl, Tl(NCS),
and TlCl(NCS)- were evaluated from the temperature dependence of the
stability constant s.741
The fusion diagram of the AgBr-TlBr-CsBr system has been reported.742
Far4.r. and Raman spectra of orthorhombic and cubic phases of thallium(r)
iodide have been obtained in the range 4-570 K, and assigned in terms of the
optical modes of these systems.743
Radioanalytical methods for the determination of intermolecular interactions have been studied using AgI-TI1-(l3lI), and Hg12-TlI-(1311) as model
systems, and comparing the results with X-ray analysis and m i ~ r 0 - d . t . a . ~ ~ ~
Other Thallium Compounds.-The
electrical resistivities of K-TI alloys
over a wide range of compositions have been measured.745The results suggest
that a high degree of localized electron bonding occurs in the liquid alloy
at a potassium mole fraction of 0.5.It is possible that the type of bonding is
similar to that occurring in the solid intermetallic compound KTl, which
crystallizes at lower temperatures.745
Tl(VS), a homologue of lautite, CuAsS, may be synthesized by slowly
heating TlS V powder at 200 ' C , under vacuum in a sealed silica tube.746
The m.p. of Hg5T1, rises with pressure, with a slope of 3.44 OC kbar-l, giving
a straight-line plot up to at least 35 kbar. No evidence was found for disproportionationation of the Hg5T12in the pressure range
Thermodynamic functions have been calculated for the Hg-TI system
over the temperature range 257-583 K.748
738
739
740
741
742
743
744
745
746
747
748
T. E. Alekseeva, N. F. Arkhipova, and V. A. Rabinovich, Russ. J . Inorg. Chem., 1972,

17, 140.
Yu. P. Afinogenov, Russ. J . Inorg. Chem., 1972, 17,908.
S. Sakka and J. D. Mackenzie, Bull. Chern. Sac. Japan, 1973, 46, 848.
V. A. Fedorov, I. D. Isaev, A. M. Robov, A. V. Vertiprakhov, and V. E. Mironov,
Rum. J . Inorg. Chem., 1972, 17,495.
S. D. Dionis'ev and A. V. Buryakov, Russ. J. Inorg. Chem., 1972, 17, 905.
R. P. Lowndes and C . H. Perry, J . Chem. Phys., 1973, 58, 271.
R. DespotoviC, Croat. Chem. Acta, 1972, 44, 341.
S. Aronson and B. Rider, J. Less-Common Metals, 1973, 31, 317.
J. K. Korn and L. Fournks, Cornpt. rend., 1973, 276, C, 1521.
P. W. Richter and C. W. F. T. Pistorius, J . Less-Common Metals, 1972, 29, 217.
Y.Claire, R. Castanet, and M. Lafftte, J . Less-Common Metals, 1973, 31, 83.
Elements of Group IV
BY
P.
G. HARRISON AND
P. HUBBERSTEY
1 Carbon
The extent of the inorganic chemistry of carbon is difficult to define; for the
purpose of this Report it has been restricted, in general, to that of the allotropes of carbon, the carbides, and the non-catenated molecular carbon
species. The chemistry of the carbaboranes is omitted since it is considered in
full in Chapter 3.
The concentration of carbon on the lunar surface in the form of carbide
(as estimated from CD, relcased by DCl dissolution) and methane has been
shown to be related to the extent of exposure of the samples on the lunar
surface;l this suggests that the source of the carbon may be the solar wind. A
new liquid-liquid chemical exchange process for the fractionation of carbon
isotopes has been reported.2The closed-cycle process is based on the exchange
reaction :
Et,C(OH)12CN(xylene)
+ K13CN(aqueous) +
EtZC(OH)l3CN(xylene)
+ K12CN(aqueous)
The single-stage isotopic separation factor is 1.035 at 20 OC, with 13C concentrating in the cyanohydrin species. Cost estimates indicate that the process
(termed CYANEX) is more economical than any existing method for the
production of high-purity 13Cin large quantities. The simultaneous determination of both 3H and 14C in very small samples by liquid scintillation techA review of the crystal chemistry of the
niques has also been effe~ted.~
Group IV elements, and their oxides, including a new approach to the
chemical crystallography of these species, has been pre~ented.~
Allotropes.-The chemistry of the allotropic forms of carbon which has been
abstracted for this Report concentrates on their structural, spectroscopic,
and intrinsic chemical properties; those papers which describesolelytheir catalytic, adsorption, diffusion, and other similar properties have been excluded.
C. T. Pillinger, B. D. Batts, G . Eglinton, A. J. T. Jull, and J. R. Maxwell, Nature
Phys. Sci., 1973, 245, 3.
a L. L. Brown and J. S. Drury, J . Inorg. Nuclear Clicm., 1973, 35, 2897.
R. Tykva, Coll. Czech. Chem. Conzm., 1973, 38, 503.
V. I. Lebedev, Souiet Phys. Cryst., 1972, 17, 33.
225
226
Vapouv-phaseSpecies. The chemical properties of carbon vapour have been

reviewed by Skell et aL5 The report describes the preparation of and compositions of the vapour and discusses the chemistry of the constituent species,
particularly C, C,, C,, and C,. Several papers describing detailed aspects of
the chemistry of these vapour-phase species have also been published.6-11
Chemical reactions of C, C,, and C,, formed by laser-induced vaporization
of either graphite or tantalum carbide, with oxygen, hydrogen, or methane
have been studied by means of time-resolved mass spectrometry and gasphase titrations in an attempt to determine the relative abundances of these
three species in the vapour phases (Table 1). The techniques developed and
Table I Relative abundancesof the vaporized species C, C2,and C,

Substrate Relative abundances
Graphite
TaC
1.0
1.0
c2
1.4
0.059
cs
17
2.2
results obtained in this study are considered to provide a foundation for

evolving the elementary reactions of carbon atoms and molecules and for
determining the vapour compositions of graphites and carbides at very high
temperatures. The products of the reaction of carbon vapour species, produced with a carbon arc, with atomic lithium have been characterized by
mass-spectrometric analysis of their hydrolysis products.' It is inferred from
the hydrolysis products (major constituent, C,H,; minor constituents, CH,
and C,H,) that the major product of the reaction is Li,C,. This product was
further characterized by treatment with ClSi(CH,),; the compound (%Me,),C,, analysed by mass and n.m.r. spectra, was obtained.
Skell et aZ.8*9
have investigated the reactions of diatomic carbon, produced
in a carbon arc under high vacuum, with simple organic compounds at
surfaces cooled by liquid nitrogen. The reaction with alkanes8 and ethers8
gives rise to allenes as well as acetylene, whereas the reaction with propylene9
(two moles) yields 5,6-niethano-1,4-heytadienes.
A chemical method for the generation of atomic carbon,1 based on the
thermal decomposition of 5-tetrazolyldiazonium chloride (Scheme l), has
Scheme 1
P. S. Skell, J. J. Havel, and M. J. McGlinchey, Accounts Chem. Res., 1973, 6 , 97.
R. T. Meyer, A. W. Lynch, and T. M. Freese, J. Phys. Chem., 1973,77, 1083.
L. A. Shimp and R. J. Lagon, J. Amer. Chem. SOC.,1973, 95, 1343.
P. S. Skell, F. A. Fagone, and K. J. Klabunde, J. Amer. Chem. SOC.,1972,94,7862.
P. S. Skell, J. E. Villaume, and F. A. Fagone, J. Amer. Chem. SOC.,1972, 94, 7866.
lo P. B. Shevlin, J. Amer. Chem. SOC.,1972, 94, 1379.
11 S. Kammula and P. B. Shevlin, J. Amer. Chem. SOC.,1973, 95, 4441.
227
been described. The decomposition has also been studied in the presence of
added gases (CO, CH,, and 02).11 The products of the ensuing reactions are
collected in Table 2. The formation of carbon suboxide, C,O,, was studied in
Table 2 Products of the reaction of atomic carbon with CO, CH,, and O2
Reacting gases
co
CH4
co + 0
CO
CO
Products
c 3 0 2
CZHl
2
+ CHI
+ CzH4
c 3 0 2
C302,CHz=C=O, C2H4,CzHB
CsOz, CHz=C=CHz, CH3CrCH
detail and the following reaction pathway postulated:
c + co -+ c=c=o
c==c=o+ co -+ o=c--c=c=o
Diamond. The synthesis of both natural12 and synthetic13-19 diamond has
been the subject of several investigations. In a discussion of the possible
natural routes to diamond, Galimov suggests that synthesis may occur under
conditions of cavitation occurring in a fast-moving magmatic melt flowing in
kimberlite pipes.12
Deryagin and Fedoseev have developed a technique for the growth of
diamond on seed crystals from carbonaceous gases, particularly CH,, below
atmospheric pressure.13-ls They have studied the effect of various parameters,
including the seeding diamond powder layer thickness, the CH, flow rate,
and the degree of dispersion, on the growth kinetics of the diamond.14J5
The main obstacle to this synthetic route is the fact that graphite is formed
in the reaction unless special measures are taken to prevent its f0rmati0n.l~
A separate investigation of the theoretical and experimental problems
relating to simultaneous formation of diamond and graphite on the surface
of the diamond crystal seeds has thus been effected to discover the optimum
conditions for the growth of diamond from carbonaceous gases.16 It has also
been established that the growth process under the conditions employed is
accompanied by a separation of the carbon isotopes.16
The growth of diamond in metal-carbon systems under superhigh pressures
has been observed on a substrate (seed crystals of synthetic diamond) in the
form of single crystallites, as discrete linear series of crystals, or in groups of
E. M. Galimov, Nature, 1973, 243, 389.
B. V. Deryagin and D. V. Fedoseev, Carbon, 1973, 11,299.
B. V. Deryagin, D. V. Fedoseev, and K. S. Uspenskaya, Russ. J. Inorg. Chem., 1973,
47, 13.
l6 D. V. Fedoseev, B. V. Deryagin, V. P. Varnin, and K. S. Uspenskaya, Russ. J. Znorg.
Chem., 1973,47, 15.
l6 D. V. Fedoseev, V. P. Varnin, and B. V. Deryagin, Russ. J . Znorg. Chem., 1973,47,17.
l7 Yu. A. Litvin, V. 1. Butuzov, E. M. Nikiferova, and S. I. Furergendler, Soviet Phys.
Cryst., 1973, 18, 278.
L. E. Shterenberg, V. N. Slesarev, and L. F. Vereshchagin, Russ. J . Inorg. Chem.,
1972, 46, 847.
la F. P. Bundy, Nature, 1973, 241, 116.
la
la
l4
16
228
crysta1s.l Two studies of the efficacy of metal catalysts in the preparation of

diamond have been effected.18J9It was concluded from a study of diamond
formation from the systems18Fe-C, Fe-C-Al, Fe-C-B, Fe-C-Mg, Fe-C-Si,
Fe-C-Cr, Fe-C-Ni, Ni-C-S, and Ni-C-CaSi, that the addition of silicon,
aluminium, magnesium, or nickel to iron causes an increase in the amount
of diamond synthesized relative to the amount formed in the Fe-C system.
Furthermore, in an investigation of high-pressure diamond synthesis in
the presence of nonconventional metallic catalystslS (Ni, Pt, Cu, and
Cu-Ni alloys containing 95 % and 99% Cu) the results are thought to
substantiate the suggestion that a catalyst solvent for the graphite-diamond
reaction must be both a carbon solvent and a diamond nucleant. In this latter
investigation, other types of catalyst solvents, including oxidesls (PbO,
HgO, and CaO), were tested.
In a theoretical investigation20of the electronic structure of diamond, its
valence bands have been determined using a linear combination of bonding
molecular orbitals formed from s-p hybridization of the 2s, 2p HartreeFock atomic orbitals of the isolated carbon atom.
Two physicochemical investigations of defects in diamond have been carried
As the result ofan investigation of thechangesincathodoluminescence
out.21*22
of diamond caused by deformations,21it is suggested that the technique is a
rapid method for detecting defects and flaws (mechanical damage) in diamond
that are otherwise not readily visible. The GR1 radiation-damage centre in
diamond has been studied by means of optical absorptions and studies of
uniaxial stress.22A comparison of the experimental results with theoretical
treatments of intrinsic defects in diamond suggests that the GR1 centre is
probably the neutral vacancy.22
Graphite. Although graphites and carbons are generally assumed to be
chemically pure carbon, it is known that their physical properties are determined by specific hydrocarbon starting materials and the various processing
techniques used in chemical synthesis, In order to assess the relative effect of
these impurities, which remain in commercial graphites and carbons after
preparation, the absolute amounts of hydrogen and hydrocarbon in several
different samples have been determined.23The data show the total hydrogen
contents ranging from 100 to 1000 p.p.m. in the carbons and 5-200 p.p.m.
in the graphites.
Several structural investigations of graphites and carbons have been
carried O U ~ . ~The
~ - results
~ ~
of a further X-ray diffraction investigation of the
2o
21
2a
23
24
25
26
P. W. Kervin and E. E. Lafon, J. Phys. Chem., 1973, 58, 1535.

M. Casey and J. Wilks, Nature, 1972, 239, 393.
C. D. Clark and J. Walker, Proc. Roy. SOC.,1973, A334, 241.
R. T. Meyer, A. W. Lynch, J. M. Freese, M. C. Smith, and R. J. Imprescia, Carbon,
1973, 11, 258.
S. Ergun, Nature, Phys. Sci.,1973, 241, 65.
A. V. Kurdyumov, Soviet Phys. Cryst., 1973 17,534.
Y u . G . Poltavtsev, V. P. Zakharov, and V. M. Pozonyakova, Soviet Phys. Crysr,
1973, 18, 270.
Elements of Group I V
229
molecular structure of graphite have been reported by E r g ~ nIn. ~an~attempt
to resolve which of the previously proposed 1,3- and 1,4-quinoidal and
hexagonal molecular structures of graphite is adopted, the experimental
diffraction results have been compared with the theoretical data derived for
the postulated structures. Surprisingly, it is concluded that the structure of
graphite is best represented by the 1,Cquinoidal structure first proposed by
Pauling.
An X-ray diffraction study of the influence of layer-packing defects of
different kinds in graphite structures on the broadening of the hkl lines has
been reported;25it has been shown that as a result of compression there is a
marked increase in the concentration of packing defects, particularly in the
rhombohedra1modification. The results of an electron diffraction analysis of
an amorphous film of carbon have shown that the only similarity between the
structure of amorphous surface films and graphite is the similar location of
the atoms in the first three co-ordination spheres.26
Several papers reporting the results of investigations of the paramagnetism
of carbons have been p~blished.~~-~O
An e.p.r. study of the paramagnetic
properties of a carbon black (P33) has been carried out as a function of
temperature;2s it has been shown that the paramagnetism is due to the
existence of two spin centres in strong interaction:
(1) localized centres which follow Curies Law, and
(2) free carriers which obey Pauli paramagnetism.
The variation of the magnetic anisotropy of a family of pyrocarbons has been

studied as a function of temperature and extent of graphitization;29a correlation between the variation of this parameter with the positive magnetoresistance of the same sample is proposed. The paramagnetic properties of
crystalline graphite samples irradiated with heavy ions (1 MeV protons,
deuterons, and helium ions) at 77 K have been studied by e.s.r. spectromet1y.3~The electron spin centres produced by the radiation are thought to
be localized, as opposed to the conduction-type electrons in unirradiated
graphite; these data are consistent with the hypothesis that electrons are
trapped at the interstitial defect sites in tracks left by the bombarding
particles.
In an attempt to understand further the structures of coals, the 13C n.m.r.
spectra of a series of four coals were compared with the corresponding
spectra of gem quality diamonds (chemical shift 156 f 3 p.p.m. from CS2)
and powdered natural graphite31 (chemical shift 35 p.p.m. from CS2). The
spectra were rationalized in terms of increasing carbon aromaticity with
increasing coal rank, leading finally to the formation of graphite-like structures. The chemical shift in diamond was found to agree well with empirical
27
28
3O
S Orzeszko, Carbon, 1973, 11, 72.

P. Delhaes and F. Carmona, Carbon, 1972, 10, 677.
P. De Kepper, P. Delhaes, and H. Gasparoux, Compt. rend., 1973, 276, C , 1369.
V. P. Virmani, J. D. Zimbrick, and E. J. Zeller, Carbon, 1972, 10, 613.

230
predictions based on prior studies of pure aliphatic and aromatic hydrocarbons; the spectrum of graphite reflects both a chemical-shift anisotropy
and the semiconducting nature of the material.31
Vitreous Carbon. Ergun and his co-workers have recently attempted to define
the structure of glassy carbon using a profile-matching technique. The
structure of a heat-treated (-3000 "C) glassy carbon produced from a polymer of furfuryl alcohol has been determined using a Fourier-transform
technique.32The stacking of layers was found to be extensive but faulty, the
mean spacing between faults being ca. 21 A. The mean interlayer spacing
was found to be 3.42 f 0.03 A. It can be concluded,33from a comparison
of the experimental data with the theoretical intensity profiles obtained from
both completely resonating and quinoidal hexagonal rings, that completely
resonating but distorted rings predominate, the distortion being severe
enough to make it very difficult if not impossible to define precisely the twodimensional lattice. Thus this particular glassy carbon can be described as
being made up of a folded network of layers of a completely resonating
st r ~ c t u r e . ~ ~
Carbyne. The crystalline structure of carbyne, the new carbon allotrope, as
determined from X-ray powder diffraction data has been re-evaluated.%
Although previously considered as a single-phase system, excellent agreement
between the experimental and theoretical data has now been obtained on the
assumption that there are two hexagonal crystalline modifications of carbyne
(a-and p-carbyne) with the cell parameters shown in Table 3. Evidence is
Table 3 Cellparameters of a- and p-carbyne

alA
CIA
a-carbyne
8.92
15.36
p-carbyne
8.24
7.68
also put forward for the transformation of a-carbyne into the more dense
p-modification when the mixture is heated for five minutes at 1800 "C and 90
kbar pressure.34
Carbon Fibres. Although a substantial amount of research has been carried
out on carbon fibres, very little is of direct relevance to the inorganic chemist.
Even those structural investigations which have been carried
are
31
3a
33
3p
36
38
37
38
H. L. Retcofsky and R. A. Freidel, J. Phys. Chern., 1973, 77, 68.

S. Ergun and R. R. Schehl, Carbon, 1973,11, 127.
S. Ergun, Carbon, 1973, 11,221.
V. I. Kasatochkin, V. V. Korshak, Yu. P. Kudryavtsev, A. M. Sladkov, and I. E.
Sterenberg, Carbon, 1973, 11, 70.
M. Stewart, 0. Zubzanda, and M. Feughelmon, Nature, Phys. Sci., 1973, 242, 42,
R. E. Bullock, D. E. Gordon, and B. C. Deaton, Carbon, 1973, 11, 418.
A. N. Ainscough, D. Dollomore, and G. R. Heal, Carbon, 1973, 11, 189.
J. B. Donnet, A. Voet, H. Dauksch, P. Ehrburger, and P. Marsh, Carbon, 1973,11,
430.
231
primarily interested in the morphology of the fibres rather than their detailed
molecular structures,
Sur~ace, Adsorption, and CataZytic Studies. Although there is much published

data on the surface properties (including their adsorption and catalytic
properties) of carbon allotropes, particularly graphites and carbons, all but a
few of these published data fall outside the scope of this review. The chemical
nature of the functional groups present on carbon surfaces has been examined
by several different techniques.3944 It has been shown40that the method of
oxidation (by either atmospheric oxygen, nitric acid, hydrogen peroxide,
or sodium hypochlorite) of both charcoals based on phenol aldehyde resins
and ashless charcoals has a significant influence on the porous structure of
the oxidized charcoals, the ability of their surface functional groups for
dissociation, and their ion-exchange capacity. As a result of the observation
that the adsorption of benzene on a selection of carbon blacks differs with
different surface functional groups, it is suggested that the use of benzene
isotherms for estimating surface areas or pore volumes of carbons must be
considered with caution.41Thus the presence of C0,-complex, which imparts
polar and hydrophilic character to the carbon surface, suppresses the adsorption of benzene but the presence of CO-complex enhances the adsorption.
The additional adsorption amounts approximately to one molecule of
benzene per quinonic oxygen; this is indicative of the probability of interaction of the benzene r-electrons with the partial positive charge on the
carbonyl carbon atom.
The results of an examination of the reaction of 2,2-diphenylpicrylhydrazyl
(DPPH) on carbon-black surfaces are thought to give conclusive evidence
that this reaction can be used for the determination of the number of hydroquinone groups present on their surfaces.42DPPH was observed not to bind
chemically to the surfaces of the carbon blacks but to abstract hydrogen
atoms, giving the corresponding hydrazine; oxidation of the carbon with
reagents such as hydrogen peroxide was found to render the specimen more
reactive to DPPH than untreated carbons.
Surface unsaturation in microcrystalline carbons, as measured by the
fixation of bromine from aqueous solution, is thought to arise from the
elimination of acidic C0,-complexes, the elimination of two moles of complex
generating one ethylenic bond.43This is said to be a definite quantity characteristic of a carbon, and it can be enhanced by surface oxidation (treatment
with potassium persulphate) followed by evacuation.
39
A. N. Tomashevskaya, I. A. Tarkovskaya, V. E. Goba, and D. N. Strazhesko, Russ.
J. Phys. Chem., 1972, 46, 1213.

40
41
42
43
4p
I. A. Tarkovskaya, D. N. Strazhesko, L. N. Grashchenkova, P. I. Kostyuchenko, and

V. E. Goba, Russ. J. Phys. Chem., 1972, 46, 1215.
B. R. Puri, B. C. Kaistha, Y. Vardhan, and 0. P. Mahajan, Carbon, 1973, 11, 329.
K. Ohkita and N. Tubokawa, Carbon, 1972, 10, 631.
B. R. Puri, 0. P. Mahajan, and D. L. Ghandi, Indian J. Chem., 1972,10, 848.
V. E. Goba, L. V. Guroshko, and E. S. Matskvich, Russ. J . Phys. Chem., 1972, 46,
1466.
232
The effect of methylation (treatment with a solution of diazomethane in
ether) on the properties of oxidized charcoals has been found to be to enhance
by ca. 50% the degree of adsorption of anions from hydrochloric acid
solutions.44This is thought to be due to the reduction of molecular oxygen on
the carbon surface by the acid, which is not observed in the case of untreated
oxidized carbon.
The adsorption characteristics of fluorine on graphite
bromine
on pyrocarbons,46and nitrogen, hydrogen, carbon monoxide, argon, oxygen,
and ethylene on pyrolysed cokes: graphitized by calcination at 2700 C,
have been studied. The adsorption of fluorine on graphite was found to be
irre~ersible,~~
a C-F bond with bond energy similar to that in fluorocarbons
being formed. On the other hand, the bromine adsorption was r e v e r ~ i b l e , ~ ~
the apparent activation energies of 1-2 kcal mol-l (adsorption) and 15-25
kcal mol-l (desorption) being derived from the data. The hydrogen was
adsorbed in two different forms on the surface of the coke.47At low pressures
the hydrogen coverage corresponded to one mole of hydrogen per two atoms
of surface carbon, whereas at higher pressures there was a 1:1 ratio.
An interesting application of the adsorption properties of carbons involved
an attempt to remove mercury from atmospheric pollutants using sulphurized
charcoal at 150 0C.48The extent of mercury removal from the contaminated
streams increased with increasing sulphur content, strongly suggesting that
the mercury reacts with the sulphur present on the carbon surface to form
mercuric sulphide.
Oxidation Studies. In a theoretical analysis of the thermodynamics of the
graphite-oxygen reaction in the presence of transition-metal oxides, Harris49
challenges the correlation of Heintz and Parker50 in which the activation
energies of the reaction are correlated with the lattice energies of the metal(11)
oxides. Although Harris49 postulates that a better correlation is obtained
using estimated lattice energies of the metal(1) oxides, he does suggest in
conclusion that a genuine correlation between transition-metal oxide lattice
energies and the activation energies for the graphite-oxygen reaction has not
been satisfactorily demonstrated.
Conclusions from recent studies of the mechanism of the oxidation of
carbons by molecular oxygen have been presented51which suggest that the
initial part of the reaction pathway involves the interaction of the oxygen
molecule with a spin centre in the carbon, with the formation of a peroxyradical C(O,)*. The next stage involves the dissociation of this species into
two atomic species C(O),, which are thought to be mobile over the carbon
surfaces. It is from these dissociated species that the products of the oxidation,
N. Watanabe, H. Takenaka, and M. Takashima, Nippon Kagaku Kaishi, 1973,487.
A. Marchand, J. C. Rouillon, and F. C. DArcollieres, Carbon, 1973, 11, 113.
47 R. E. Mardaleishvili and Zh. Ya. Smorodinskaya, Doklady Chem, 1972, 204,425.
48 R. K. Sinha and P. L. Walker, Carbon, 1972, 18, 754.
49 P. S. Harris, Carbon, 1972, 10, 643.
so E. A. Heintz and W. E. Parker, Carbon, 1966,4473.
s1 H. Marsh and A. D. Foord, Carbon, 1973, 11,421.
45
46
233
viz. CO and C02, are produced:
In a study of the oxidation of several types of carbons using potassium

permanganate dissolved in sulphuric acid with sodium nitrate as catalyst,
the experimental results were best rationalized by introducing two distinct
reaction stages during the 0xidation.5~In the first stage, two simultaneous
reactions take place: (a) the formation of lamellar graphite oxide, and (6)
direct oxidation of the carbon into carbon dioxide. During the second stage
only graphite oxide lamellae remain, formed from well-organized carbon
planes, the oxidation rate of these lamellae into COzdepending on the nature
of the initial carbon.
Kinetic53 and X-ray photoelectron spectros~opic~~
(XPS) studies of the
reaction of oxygen with basal faces of graphite have been effected. The results
of the kinetic
(temperature range 1100-2000 K) indicate that the
overall process lies in the transition regime between the limits of chemical and
has revealed the first
diffusional control for the oxidation. The XPS
direct evidence of chemisorption of atomic oxygen on individual faces of
single crystals of graphite; the degree of uptake is enhanced if the basal
surface is first subjected to argon-ion etching followed by exposure to molecular oxygen. A complementary XPS study of the carbon and oxygen 1s
peaks of samples of carbon fibres which have been subjected to differing oxidation procedures has been
The carbon 1s spectra so obtained consist of
two peaks, the secondary peak position varying with oxidation procedure.
The two secondary peaks (Table 4) are attributed to carbons of the type
C=O and C-OH.
Table 4 XPS of oxidized carbon fibres
Carbon 1 s peak,
energyleV
284
286.1
287.7
Assignment
C
C-OH
c=o
It is concluded that XPS allows an effective means of determining the type of

carbon present and the results of any effective oxidation.
The reaction of ozone with carbons has been the subject of three investigat i o n ~ . ~ ' +The
~ ~ kinetics of the gas-solid reaction at ambient temperature
52
53
54
56
56
5'
P. Ehrburger and J.-B. Donnet, Carbon, 1973, 11, 309.

T. R. Acharya and D. R. Olander, Carbon, 1973, 11, 7 .
M. Barber, E. L. Evans, and J. M. Thomas, Chem. Phys. Letters, 1973, 18, 423.
J.-B. Donnet, H. Dauksch, J. Escard, and C. Winter, Compt. rend., 1972,275, C, 1219.
V. R. Deitz and J. L. Bitner, Curbon, 1973, 11, 393.
J.-B. Donnet, P. Ehrburger, and A. Voet, Carbon, 1972, 10, 737.
J.-B. Donnet, M. Rigaut, R. Furstenberger, and P. Ehrburger, Carbon, 1973,11,68.
234
have been monitored by both U.V. absorption and i.r. detection of COz
formation in flow experiment^.^^ Interpretation of the results leads to the
following reaction sequence, in which the early stages of the overall reaction
consist of either oxygen abstraction from an ozone molecule (at site Cn~)
or
addition of the ozone molecule to a surface double-bond (site C,@).Thus:
The products of reaction (2) can lead to subsequent surface changes, yielding
coz :
Cn*.
O3 -+ Cn-lm - 0
C02
(3)
The surface products of reactions (1) and (3) may have similar chemical
properties, and CO could form as follows:
A kinetic study of the oxidation of carbon blacks in aqueous media5' by ozone

shows two distinct and simultaneous reactions : (a) formation of degradation
products which are partially oxidized to COz, and (b) a direct oxidation into
C02.It has also been shown that the degradation products, which have been
the subject of a complementary e.p.r. study,58arise from the less organized
areas of the carbon-black particles. The relation established between the
fraction degraded by oxidation and the disorganization factor (which is
directly related to the interplanar d-spacing of the specimen) leads to a classification of the carbon blacks according to the degree of perfection of their
interplanar d-spacing distribution pattern.
The electrochemical oxidation of carbon black in 96% phosphoric acid
has been studied at 135 0C.59Two anodic processes were observed to occur:
(a) the formation of a surface oxide, and (b) the evolution of CO,. Both
processes decreased with time but at different rates, so that CO, evolution
eventually became the major reaction.
In a theoretical treatment of the oxidation of carbon in CO-CO, mixtures,
GrabkeG0suggests that the reaction can be discussed assuming the mechanism :
CO,
O(adsorbed)
CO
+ C -+CO
+ O(adsorbed)
(6)
(7)
The treatment issupported and supplemented bymeasurementsof both partial

reactions at different carbons60(electrode graphite, charcoal, natural graphite,
and iron-doped graphite). From these kinetic studies it can be concluded that
reactions (6) and (7) take place at different sites; nevertheless the kinetics of
both reactions are correlated since a uniform oxygen activity is established
59
K. Kinoshita and J . Bett, Carbon, 1973, 11, 237.

H. J. Grabke, Carbon, 1972, 10, 587.
EIements of Group IV
235
at the carbon surface by the interplay of the oxygen surface diffusion and of
both reactions.
In a desire to convert waste SO, into either a less noxious or a more useful
product (e.g. S or CS2),the oxidation of carbons by SO, at elevated temperatures (800-950 "C) has been investigated;61the reaction is shown to involve
the five reactions (8)-(12).
+ 2SOa
2C
c + s2 + coz
c
+ 2cos
+
c+
2COa
2cos
cs2
c02
--j
2co
s
2
--j
cs2
+ SB
+ 2co
(8)
(9)
(10)
The reactivity of various carbons as reducing agents for Cr203has been

investigated;62the results show that the relative reactivities of the carbons in
this solid-solid reaction are comparable with those previously observed in
the course of studies with oxygen or even iron oxides (i.e. reactions directly or
indirectly operating with the gaseous phase).
Carbides.-The crystal chemistry of ternary and more complex carbides has
been reviewed.63The dissociation energies of gaseous metal dicarbides have
also been reviewed and compared with those of the corresponding chal. ~ ~ results of two
cogenide systems for which information is a ~ a i l a b l e The
mass-spectrometric investigations of the atomization energies (AH,Ot,,,o),
dissociation energies (03,
and enthalpies of formation (AH;b,,,,8)~fAlC,,65
Al,C2,65A ~ A u C , , ~ ~ RhC,66and RhC,66 are tabulated in Table 5.
Table 5 Thermochemical data of gaseous metal carbides
A~f:ttom.ol
Carbide
A1C2
A12C2
AlAuC,
Ticz
RhC
RhC,
kJ moi-1
1104 f 21
1507 f 25
1418 f 21
1159 f 8
1033 f 21
081
kJ mol-1
514.2 f 21 (Al-C)
459
(Al-C)
365
(AU-C)
565 f 17 (Ti-C2)
577.4 f 8.4 (Rh-C)
439 f 21 (Rh-C,)
AH106rm12981
kJ mol-1
729.7 f 8.8
686.6 f 9.6
941 f 21
Re6
65
65
65
66
66
66
A new 1 89-layered rhombohedra1 modification of silicon carbide has been

discovered as a small region of a well-ordered 21R structure crystal.67This is
one of the few examples of silicon carbide structures based on a phase, 21R,
other than one of the usual basic structures 6H, 15R, and 4H. The behaviour
61
62
6s
64
65
66
g7
J. D. Blackwood and D. J. McCarthy, Austral. J. Chem., 1973, 26, 723.

R. Fremont-Lamouranne, Y. Grillet, and H. Guerin, Bull. SOC.chim. France, 1972,
3675.
H. Nowotny, Angew. Chem. Internat. Edn., 1972, 11,906.
E. E. Filby and L. L. Ames. Inorg. Nuclear Chern. Letters, 1972, 8, 855.
C. A. Stearns and F. J. Kohl, J. Phys. Chem., 1973, 77, 136.
D. L. Cocke and K. A. Gingerich, J. Chem. Phys., 1972,57, 3654.
M. Dubev, U. S. Ram, and G. Singh, Acta Cryst., 1973, B29, 1548.
236
of carbon in high-purity silicon in the dissolution and fusion of the matrix

has been studied by llC tracer techniques.68 Silicon samples containing llC
either atomistically dispersed or coagulated as Sic were prepared and subjected to dissolution and fusion experiments. Whereas in alkali dissolution
no loss of llC was observed, in HF-HN0,-KIO, dissolution and subsequent
KMnO, treatment the dispersed carbon was almost quantitatively oxidized,
but the Sic coagulates were not completely destroyed. In alkali fusion a part
of the llC was lost, and, by fusion with Pb304-B203carbon in both states
was converted into GO2.
An adherent and continuous crystal of zirconium carbide, ZrC, has been
growne9on the surface of graphite at 1100 OC in the presence of zirconium,
zirconium(1v) chloride, and hydrogen according to the equations :
+ 2Hz
+C
ZrC1,
Zr
3
3
+ 4HC1
Zr
ZrC
The reaction was found to be catalysed by the presence of chromium. In a

separate in~estigation,~~
the concentration dependence of the lattice parameters of this monocarbide, together with those of Tic, HfC, VC, NbC,
and TaC, has been investigated. It has been shown that the significant factor
affecting the parameters is whether the equilibrium M-C distance is associated with a lattice parameter greater or less than that produced by a nonscreened M-M interaction. An electron diffraction study7' of one of these
non-stoicheiometric carbides, VC,
which is cubic, and the hexagonal V2C
has also been completed.
Phase equilibria in the binary C-P72 and ternary V-C-P73
systems have
been investigated at elevated temperatures. The product of the codeposition
of carbon and phosphorus effected from a gaseous mixture of CH,, PCl,,
and H2 at deposition temperatures ranging from 1220 to 1730 OC with 1-15
vol. % PCl, in the gas mixture is a pyrocarbon containing p h o s p h ~ r u sThe
.~~
maximum phosphorus concentration which can be retained in the product,
presumably in the form of a substitutional solid solution, decreases with
increasing deposition temperature from 4-5 wt. % at 1220 OC to 0 wt. % at
1530 "C. Although no binary phases were observed in this system, an investigation of the phase equilibria in the V-P-C
ternary system using X-ray
techniques yielded five ternary phases.73 As well as V3PC,,
and V2PC
already described, V,P3C,
(a filled-up 0 8 8 type), the cell parameters for
which increase with vanadium content (Table 6), the orthorhombic v6P&&,
68
70
71
72
73
T. Nozaki, Y . Makide, Y . Yatsurugi, Y . Endo, and N. Akiyama, Bull. Chem. SOC.

Japan, 1972, 45, 2776.
L. Vandenbulke and G. Vuillard, Compt. rend., 1973, 276, C, 1759.
V. A. Tskhai, S. I. Alyamovskii, P. V. Gel'd, and G. P. Shveikin, Russ. J. Inorg.
Chem., 1972, 17, 317.
N. Terao, Compt. rend., 1972,275, C, 1165.
S. Marinkovic, C. Suznjevic, A. Tukovic, I. Dezarov, and D. Cerovic, Carbon, 1973,
11, 217.
H. Boiier, Monatsh., 1973, 104, 48.
Table 6 V,+,P&-,
237
cell parameterslA
a
Carbon-rich
Vanadium-rich
6.88 4.77
6.94 4.82
(cell parameters a = 17.12, b = 3.218, c = 13.04A), and the hexagonal

V4P2Cwere characterized. The detailed crystal structure of this latter compound has been determined7s(space group P62m, cell parameters a = 9.567,
c = 3.166A); it represents a new structure type which can be described as a
dense packing of trigonal-prismatic and octahedral building elements.
The crystal structure of chromium carbide Cr,,C, has been confirmed74
as cubic, space group F
,
3
,
with cell parameter a, = 10.650 on the basis of
X-ray single-crystal and powder diffraction data.
Ground-state RhC molecules, produced by the vaporization of a mixture
of rhodium and carbon from a graphite cell, have been trapped in Ne and Ar
matrices at 4 K.75
The electronic configuration of the molecule as determined
5 s o )some
~ , mixing
from its e.s.r. spectra is largely ( 4 d ~ ) ~ ( 4 d n ) ~ ( 4 d d ) ~ ( with
of 4do with 5so.
The cubic to tetragonal phase-transition temperatures of all the lanthanide
dicarbides (Table 7), with the exception of SmC,, TbC,, and TmC,, have been
Table 7 Cubic-tetragonal phase-transition temperatures1"C of Ianthanide

dicarbides
Dicarbide
La
Ce
Pr
Nd
Gd
Dy
Ho
Er
Lu
Transition
ternperuture 995 1090 1100 1150 1218 1250 1280 1275 1390 1690
a~certained.~~
The effect of intersolution of the dicarbides on the transition
temperature has also been investigated for a number of dicarbide pairs.
Several papers describing phase relationships in the CeSi-C,77MII-S~-C,~~
Mn-Ge-C,79 Mn-B-C,79 and Cr-B-C79 ternary systems have been published.
In the course of a mass-spectrometric study of the vapour issuing from a
graphite-lined tungsten cell loaded with pure graphite powder and 99%
pure CeSi,, a CeSiC molecule was observed and its stability determined.77
The perovskite Mn,SnC has been prepared and its structure determined as a
function of temperat~re'~
(4.2-325 K). It is cubic at all temperatures, the
crystal parameter a, (= 3.986 at 4.2 K) increasing slightly with increasing
temperature until at 292 K it undergoes a sharp variation (from 3.996 to
74
76
76
l7
78
78
A. L. Bowman, G . P. Arnold, E. K. Storms, and N. G. Nereson, Acta Cryst., 1972,

B28, 3102.
J. M. Brom, W. R. M. Graham, and W. Weltner, J. Chem. Phys., 1972, 51, 4116.
I. J. McColm, T. A. Quieley, and N. J. Clark, J. Inorg. Nuclear Chem., 1973, 35,1931.
M. Guido and G. Gigli, J. Chem. Phys., 1973, 59, 3437.
E. Fruchart, G. Lorthioir, and R. Fruchart, Compt. rend., 1972, 275, C, 1415.
G. Papesch, H. Nowotny, and F. Benesovsky, Monatsh., 1973, 104,933.

238
3.993 A) characteristic of a first-order transition. This transition is accompanied by a discontinuity of the magnetic properties of the system. In the
analogous Mn-Ge-C system79it has been observed that there is an almost
continuous transition between y-Mn(Ge, C) solid solutions and the perovskite
carbide Mn,GeC,. Investigations of the Mn-B-C7S and Cr-B-C7g systems
have shown that although carbon-boron substitution in Mn,,C, extends to
almost Mn2,C3B3,the mutual solubility of the chromium carbides and borides
is insignificant at 1000 'C.
Two investigations of oxide carbides of general interest to inorganic chemists have been reported.80i81Lanthanum oxide carbide, La20,C2, has been
prepared by a number of techniques;s0the best yields were obtained when the
reactants, in the appropriate quantities, were arc-melted under an atmosphere
of CO using a graphite electrode:
La(s)
+ La,O,(s) + ~ c ( sCq
) +La,O,C,(s)
Vapour-phase chromatographic analysis indicates the principal product of

the acid hydrolysis of La,O,C, to be acetylene, thus suggesting the presence
of Cf- units in the carbide. An X-ray diffraction study of the phase shows it to
be monoclinic (cell parameters a = 7.084 f 0.005, b = 3.994 f 0.004,
c = 7.325 f 0.007& B = 95.67 f 0.05'). From a CO equilibration study
of the reaction:
La,O,C,(s)
+ COCg)
La,O,(s)
+ 3CW
effected in a constant-volume system, the standard enthalpy of formation of

La,O,C, has been determined as -320 f 2 kcal mol-l. The resistivity of
uranium oxide carbides UC,,O,(O
< x < 0.34) has been measured as a
function of temperature (80-1200 K) and oxygen concentration.s1 The
resistivity increases with both temperature and oxygen concentration. The
authors claim that these increases are governed by the presence of both
exchange and coulombicmetal-metal and metal-non-metal interactions which
control the degree of imperfection of these compounds. The imperfection is
thought to be caused by the use of uranium Sfand 6d electrons together with
non-metal-atom 2p electrons possessing the symmetry of n-bonds.
Graphite Intercalation Compounds.-The reactions of graphitizable carbons
leading to the formation of graphite intercalation compounds have been
reviewed.82 Emphasis was placed on the insertion of alkali metals (Na),
halogens (Br,), and acids (H2S0,). The effects of electronic structure and
electron exchange on intercalation reactions were also considered.
The formation of the 'non-conducting' lamellar intercalation compounds
graphite oxides3 and graphite f l ~ o r i d has
e ~ ~been
~ ~ the
~ subject of several
82
83
86
A. D. Butherus and H. A. Eick, J. Inorg. Nuclear Chem., 1973, 35, 1925.

A. A. Larin and V. G. Vlasov, Russ. J. Inorg. Chem., 1972, 17, 153.
M. C. Robert, M. Oberlin, and J. Mering, Chem. and Phys. Carbon, 1973, 10, 141.
P. Ehrburger and J.-B. Donnet, Carbon, 1973, 11, 309.
R. J. Lagow, L. A. Shimp, D. K. Lam,-and R. F. Baddour, Inorg. Chem., 1972, 11,
2568.
239
reports. The former has been prepared during the oxidation of several types
of carbons by potassium permanganate dissolved in sulphuric acid, using
sodium nitrate as catalyst.83A new synthesis of the latter, based on a glow
discharge in elemental fluorine, has been described.84Using a fluidized-bed
reactor a configuration was chosen to optimize contact of graphite particles
with fluorine, and a total yield of graphite fluoride of 80 % was achieved. In a
second study of the carbon-fluorine system, the adsorption of fluorine on
graphite powder has been followed in the temperature range -78 to 200 OC
and at pressures up to 160 rnmHgs5 An examination of the results indicates
that the bond energy between the adsorbed fluorine and carbon atoms on the
surface of the graphite would be similar to but not as strong as C-F covalentbond formation in fluorocarbons. X-Ray diffraction patterns also show that
the interlayer structure of the graphite surface was slightly strained by the
interaction of fluorine atoms with the n--electronsof the carbon atoms.
Alkali Metals. In an attempt to establish the existence of the intercalated
compound C4K, HCrold et al. carried out a detailed experimental analysis of
the reaction of molten potassium with graphite.86Neither enthalpy analysis,
centrifugal separation, dilatometry, nor X-ray crystallography gave any
evidence for the formation of C,K.
The existence of intercalation compounds of potassium with carbon in the
form of fibres has been substantiated by Hkrinckx et aZ.S7,8sWell-defined
compounds of both the first stage, C,K, and second stage, C,,K to C,,K,
can be obtained under appropriate condition^.^^^^^ The colour of these
compounds is bronze-brown for the first stage and steel-blue to black-blue
for the second stage (cf. graphite intercalation corn pound^).^^ X-Ray studies
show that the potassium layers are hexagonal-close-packed in both stages ;
the transition from C,,K to C,& in the second stage is a result of an increase
in the concentration of randomly distributed vacancies in the two-dimensional
lattices with progressive d e s o r p t i ~ n Neither
.~~
the mechanical properties
nor the general morphology of the fibres are affected on intercalation, as
might be expected from a consideration of the wrinkled ribbon structure
model of carbon fibres.88
HCrold et aLS9have suggested that the insertion of elements into graphite
could be applied to the separation of isotopes. In a study of the equilibrium
between rubidium and the first-stage intercalation compound RbC,, it has
been shown that the inserted metal is more rich in the heavier isotope than
the free metal. A coefficient of enrichment, K , has been estimated from the
data:
K
86
13
[z]rgIcBRb
= 87Rb metal x
1,003
D. Billaud, B. Carton, A. MCtrot, and A. HCrold, Bull. SOC.chim.France, 1973, 2259.

C. Hkrinckx, R. Perret, and W. Ruland, Carbon, 1972, 10, 71 1.
A. Fourdeux and C. Hkrinckx, Nature, Phys. Sci., 1973, 242, 43.
D. Billaud, A. Herold, and F. Leutwein, Compt. rend., 1973, 277, C, 419.
240
Two groups of workers have presented conflicting reports describing the

adsorption properties of alkali-metal-graphite intercalation c o r n p o ~ n d s . ~ ~ - ~ ~
Watanabe et aLgohave studied the adsorption of hydrogen, deuterium,
nitrogen, methane, and the inert gases on first- and second-stage alkalimetal graphites, C8M and C2,M (M = K, Rb, or Cs), at 63-196 K. Hdrold
et al. have examined the adsorption of hydrogen and deuterium on both
C,Kgl and C24Kg2over the temperature range 85-123 K. Although HCroldgf
observed that the first-stage intercalated compounds C8M reversibly adsorb
hydrogen and deuterium to form ternary phases C,KH,, Watanabegofound
them to be non-sorptive. The ternary productsg1were described as either (a)
ternary insertion compounds (for smooth carbons annealed above 1600 "C)
or (6) mixtures of such compounds with crystallized KH under its classical
form (for hard carbon) or under a deformed one (for smooth carbons annealed at under 1600 "C). In the case of the second-stage compounds, C,,M,
HQoldg2concludes that the adsorption of hydrogen is essentially a physisorption process. Watanabe'sgosystematic study of the adsorption isotherms
for all the quoted systems revealed a dependence of the isotherm type and the
heats of adsorption on both the size of the gas molecules and the size of the
intercalated alkali metals. A concurrent neutron-diffraction studyw of the
system C24K-D2 has shown that the adsorption is due to occlusion of gas
molecules between the intercalated graphite layers. Watanabego has also
studied adsorption from selected gas mixtures to manifest the actual 'molecular sieving' action of both C24K (D2 N2 and D2 Ar) and C3,K
(D,
H2) (Table 8). The adsorption characteristics of both intercalation
compounds were found to be almost identical.
Table 8 Adsorption from a 1 :1 mixture of hydrogen and deuterium: final

distribution in the vapour and adsorbedphases at 90 K (adsorbent
(%3K)
Hydrogen Deuterium
Gas phase (vol. %)
Adsorbed phase (vol. %)
81
19
41
59
HaZogens, Halides, Oxides, and Acids. In a series of experiments examining

the formation of interhalogen graphite intercalation compounds, the adsorption of ClF3,93BrF3,94and IF*
:
by graphite has been studied. Since the ClF,
was adsorbed from anhydrous liquid HF it was first necessary to examine the
adsorption characteristics of the graphite-HF system;95the formation of the
91
92
93
94
95
K. Watanabe, T. Kondon, M. Soma, T. Onishi, and K. Tamura, Proc. Roy. Soc.,

1973, A333, 51.
C. Gehin and A. Herold, Bull. SOC.chim. France, 1972, 3767.
P. Lagrange, A. MCtrot, and A, Herold, Compt. rend., 1972, 275, C, 765.
A. A. Opalovskii, A. S. Nazarov, and A. A. Uminskii, Russ. J. Inorg. Chem., 1972,
17, 1366.
A. A. Opalovskii, A. S. Nazarov, A. A. Uminskii, and Yu. V. Chichagov, Russ. J.
Inorg. Chem., 1972, 17, 1227.
A. A. Opalovskii, A. S. Nazarov, and A. A. Uminskii, Russ. J . Inorg. Chem., 1972
17, 632.
241
compounds of composition C,HF (n = 4 , 5 , 6 , 7 , or 8) has been established.
Adsorption from the ClF, solutions yielded a new intercalation compound
C,4F,3HF,ClF3;93on the basis of its i.r. spectra this compound is best
designated as Cr4H2F3ClFiHF;. It has also been established that the
reaction of BrF,94 and
with graphite gives rise to insertion compounds
of composition C,,,BrF, and C,,IF,, respectively.
Intercalation of metal chlorides in graphite from both the vapour phaseS6sg7
and anhydrous thionyl chloride solutionsg8has been the subject of several
investigations. The adsorption isotherms of a series of metal chloride vapours
(AlCl,, GaCl,, InCl,, MoCl,, TaCI,, WCl,, ZrCl,, HgCl,, and SbC1,) have
been determinedg6and the results analysed in an attempt to elucidate a theory
of intercalation of these halides in graphite matrices. Gold(rI1) chloride has
been found to form several graphite intercalation compounds, of which the
most rich is of the first stage and has the stoicheiometry C,,.,AUCI,.~~The
interplanar distance of 6.80A measured in this compound is much smaller
than that of the insertion compounds of other chlorides, e.g. CrCl,, 9.45 A
and AICI,, 9.54A. Although adsorption of UCl, from anhydrous SOCl,
i.e. UCI,solutions gives rise to two first-stage intercalation
graphite and UC1,,SOC12-graphite, the metal chlorides AlCl,, NbCl,, TaCl,,
and MoOCl, are intercalated from solution without S0C1,.98 AlCl, is intercalated to the second stage and NbCl,, TaCl,, and MoOCl, to the third stage.
Chlorine which is additionally bound in the AICl,, NbCl,, and TaCl, insertion
compounds is thought to result from decomposition of SOCl,:
4SOC12
2SO2
+ SsCI2 + 3C1,
The X-ray crystal structure, electrical conductivity, and thermal stability of

the lamellar compound C,7.5Cr0,C1, have been determined.g9 The compound, which is of the third stage (with a c-axis dimension of 14.87 A) was
found to be unusually stable, and its conductivity as well as composition
shows but slight change after complete evacuation of the reacting CrO2C1,
gas.
Pure perchloric acid has been observed to react slowly with graphite at
room temperature, to give the first-stage intercalation compound Ci4.g,
Clop, 2HC104 and chlorine trioxide:loO
24.9C + 4HC104 +- C&.&10~,2HC104+ C10, + H 2 0
The interplanar distance of the product (7.85 A)is slightly smaller than that
(7.94 A) of the compound obtained by treating graphite with dilute aqueous
perchloric acid in the presence of oxidizing agents. Under similar conditions
Cl,O, does not react with graphite;loOthe reaction can be effected, however,
by the action of C120, vapour diluted with dry air on pyro-graphite. A secondstage product is obtained which, when treated with liquid Cl,07 at -20 "C,
96
97
s8
99
100
J. G. Hooley, Carbon, 1973, 11, 225.

R. Vangelisti and A. Herold, Compt. rend., 1973, 276, C, 1109.
A. Boeck and W. Riidorff, 2. anorg. Chem., 1973, 397, 199.
Y. Takahashi, H. Yamagata, and T. Mukaibo, Carbon, 1973, 11, 19.
H. Fuzellier and A. HCrold, Compt. rend., 1973, 276, C, 1287.
242
leads to the first-stage compound C12C1207.This product decomposes spontaneously at room temperature, passing through various higher intercalation
stages. As for the perchlorates, the interplanar distance varies from 7.96A
for the first stage through 7.78 A for the second stage to 7.70 A for the higher
stages.
Methane and its Substituted Derivatives.-A large proportion of recently

published literature describing the chemistry of this particular class of
compounds and of that of the other non-catenated carbon-containing species
is associated with their theoretical and spectroscopic properties; presumably
their molecular simplicity makes them ideally suited for such detailed and
complex studies. Thus, those sections discussing the literature for these
molecules are split into two, the data describing their basic chemistry being
considered after a collation of those describing their spectroscopic properties.
Methane. Altogether eight theoretical investigations of the electronic structure
of ground, excited, and ionized states of methane have been carried out ;lO1--lo*
in several instances, the results have been compared with those of the corresponding Group IV hydrides, SiH,,lo1-lo3 GeH4,l0lJo2SnH4,101and PbH4.101
One of the more fascinating of these investigationslo4involved the derivation
of LCAO-MO-SCF wavefunctions for methane both with and without the
constraint that the first two a1 MOs should be the 1s and 2s SCF AOs of the
carbon atom. Calculations were carried out for both tetrahedral and distorted
tetrahedral nuclear configurations and it was deduced that the tetrahedral
configuration is the most stable both with and without the constraint.
Furthermore, in an attempt to examine the effects of non-promotional hybridization in methane,lo4calculations were carried out in which the s-type basis
functions, and the four associated electrons, of the carbon atom were completely deleted and replaced with an appropriate nuclear charge. Again a
tetrahedral methane molecule was obtained; it was thus concluded that 2s 4
2p promotion and/or hybridization does not cause the tetrahedral structure
of methane.
An analysis of the X-ray photoelectron spectra (XPS) of analogous gaseous
compounds of carbon, silicon, and germanium has been carried out.los By
incorporating the atomic charge-potential model and both CND0/2 and
electronegativity parameter charges it has been shown that, with the exception
of SiH, and GeH,, the silicon and germanium atoms have unexpectedly high
K. Hensen, M. Achatz, and R. Miiller, Theor. Cliim. Acta, 1973, 28, 297.
W. B. Perry and W. L. Jolly, Chem. P h p . Letters, 1972, 17, 611.
lo3S. Kohda and S. Katagiri, Bull. Chem. SOC.Japan, 1973, 46, 1428.
lo4 J. Jarvie, W. Willson, J. Doolittle, and C. Edmiston, J. Chem. Phys., 1973, 59, 3020.
lo5 P. W. Deutsch and A. B. Kunz, J. Chem. Phys., 1973,59, 1155.
lo6W. Von Niessen, Theor. Chim. Acta, 1973, 29, 29.
lo7 J. C. Barthelat and P. Durand, Theor. Chim. Acta, 1972, 27, 109.
lo8W. Meyer, J. Chem. Phys., 1973,58, 1017.
lol
lo2
Elcments of Group IV
243
negative charges. The results are consistent with the existence of significant
p ~ - - d r bonding in silicon and germanium compounds (except SiH, and
GeH,) and its absence in all analogous carbon compounds, including
methane.
Several high-resolution vibration-rotation spectra (ix. and Raman) of
selected bands of methanelog-l13 and [2H2]methane114J15have been reported.
Theoretical analyses of both the i.r. band contours of methane in gaseous and
liquid mixtures116 and the rotational motion of methane molecules embedded
in inert-gas matrices (Ar, Kr, and Xe)l17have been carried out; the computed
i.r. spectra are in satisfactory agreement with those experimentally determined.
A structural analysis118 of solid methane and [2H,]methane has been
attempted on the basis of an interpretation of extensive i.r. absorption
measurements of CH,, CD,, and mixed isotopic crystals containing CH,,
CD,, CHD,, and CH,D at low concentration in matrices of light and heavy
methane in crystalline phases I and 11. The spectra indicate that solid CH,
and CD, have the same crystal structures in phase I as in phase 11. In phase I,
there is apparently considerable motion; in phase I1 there exist two types of
molecular sites : some molecules undergo quantized rotation similar to that
found in noble-gas matrices while others order with a local symmetry that is
slightly distorted from Tdto DZd.
The electron-impact spectra of methane have been compared with those of
tetraflu~romethanell~
and silane;120 the spectra of all three molecules have
been compared with the corresponding photoionization and photoelectron
spectra, The relatively new technique of threshold electron-photoion coincidence mass spectrometry has been applied to, inter alia, methane and [2H4]methane.121The technique permits the direct determination of the kinetics of
dissociation of a molecular ion as a function of that ion. Thus, fragmentation
of CHZ and CDZ has been determined as a function of internal energy and
the results have been compared to previous photoionization, charge-exchange,
and photoelectron-photoion coincidence mass-spectrometric results and to
theoretical models.lZ1
Very few data describing the inorganic reactions of methane have been
reported in the literature. The oxidation of methane has been the subject of
B. Bobin and K. Fox, J. Chem. Phys., 1973, 58, 1771.
loo
H. Berger, M. Faivre, J. P. Champion, and J. Moret-Bailly, J. Mol. Spectroscopy

1973, 45,298.
111
L. A. Pugh, T. Owen, and K. N. Rao, J. Chern. Phys., 1973,59,
1243.
J. Susskind, J. Mol. Spectroscopy, 1973,45, 457.

118 J. Cadot and R. Delorme, J . Mol. Spectroscopy, 1973, 45,443.
lla
J.-C. Deroche and G. Graner, J. Mol. Spectroscopy, 1973,45, 322.

J.-C. Deroche, Compt. rend., 1973,275, B, 479.
n6T. E. Eables and R. E. D. McClung, J. Chem. Phys., 1973,59,435.
117 K.Nishiyama and T. Y. Amamoto, J. Chem. Phys., 1973,58, 1001.
118 C. Chapados and A. Cabana, Canad. J. Chem., 1972, 50, 3521.
W. R. Harshbarger and E. N. Lassettre, J. Chem. Phys., 1973, 58, 1505.
lao
J. D. Morrison and J. C. Traeger, Internat. J. Mass Spectrometry Ion Phys., 1973, 11,
114
116
289.
R. Stockbauer, J . Chern. Phys.,
lal
17
1973, 58, 3800.
244
four
The kinetics of the slow oxidation of methane in a
dynamic system over the temperature range 584-730 OC and at atmospheric
pressure have been examined;122it was deduced that the reaction is first-order
with respect to methane and second-order with respect to oxygen. The nitricacid-initiated oxidation of methane has also been investigated in a dynamical
system at 557 0C.123Gas-phase reactions of O(lD),produced by photolysis of
both nitrous oxide124 (using 1849 8, light) and carbon dioxide'26 (using
1633 A light), with methane have been studied. In the N,O-CH, system124
at low pressures the main path of the reaction was to formmethylandhydroxyl
radicals, which ultimately produce C2H,. Molecular elimination giving hydrogen and formaldehyde occurred to an extent of 9 %, which is comparable
to the ratio obtained when the reaction takes place in liquid argon at 87 K.
Photolysis of the C02-CH, mixturesf25at 873 K gave similar products to
those of the reaction of O(3P)with methane; very little or no methanol,
obtained by stabilization of the complex formed by an insertion reaction of
O('0) atoms, was obtained.
A y-ray and electron-pulse radiolytic study of aqueous methane has been
effected.126The absorption spectrum of the methyl free radical has been
measured in the range 210-270 nm [at 210 nm, &(CH3)= 850 1 mol-l cm-l),
and by determining its rates of formation and decay the rate constants for the
reactions :
.OH
*CH3
+ CHI
+ -CH3-+
*CHS
C,H,
+ HZ0
have been established. A theoretical analysis of the thermal yields in the

reaction of 8oBr activated by the (n, y ) process with methane and [2H4]methane has also been carried
The pyrolysis of a diluted mixture of equimolar CH, and CD, was performed in a shock tube between 1500 and 1600 K and the products were
quantitatively determined.128From the hydrogen isotopic distribution of the
products, methyl radical formation was confirmed as the initiation step
of CH, pyrolysis;
CH, -+ .CH8
+ H*
The heat of combustion of, inter aliu, methane has been measured at 25 "C
and atmospheric pressure using a flame calorimeter.129The value obtained,
AHi(CH4, g) = -890.71 f 0.38 kJ mol-l, differs slightly from the previously accepted values but is in better accord with the requirements of the
Allen bond-energy scheme.
12z
123
124
125
126
12'
12*
129
I. G. Murgulescu and M. G. Buzeganu, Rev. Roumaine Chim., 1972, 17, 1637.

I. Iosif, 1. A. Schneider, and C. Volanschi, Rev. Roumaine Chim., 1973, 18, 195.
C.-L. Lin and W. B. Demore, J. Plzys. Chern., 1973, 77, 863.
J. N. Falconer, D. E. Hoare, and R. Overend, J.C.S. Faraday I, 1973, 69, 1541.
G. C. Stevens, R. M. Clarke, and E. J. Hart, J . Phys. Chern., 1972, 76, 3863.
M. Saeki and E. Tachikawa, Bull. Chem. SOC.Japan, 1973, 46, 839.
Y . Yano, Bull. Chem. SOC.Japan, 1973, 46, 1619.
D. A. Pittam and G. Pilcher, J.C.S. Faraduy 1, 1972, 68,2224.
245
The chemical reactions of methane in a triboelectric discharge have been

studied.13* The effects of physical parameters (e.g. surface area and surface
nature) on the discharge process, which arises from the intermittent contacting
of mercury with a glass surface, have been examined. (The discharge results
from the accumulation of high densities of static charge at the interface by the
transfer of electrons from the metal to the glass.) The effects of inert gases and
oxygen on the process have also been studied and the results of these exgeriments together with a comparison of the prcducts formed in other decomposition processes suggest that the radicals C H , and CH, are important
intermediates in the triboelectric process occurring in methane.130
Halogenomethanes. Several theoretical studies of the electronic structures of
the halogenomethanes have been ~ n d e r t a k e n . l ~ lSCF-MO
- ~ ~ ~ calc~lationsl~~
of the electric dipole moments and nuclear quadrupole coupling constants of
a series of isoelectronic molecules including methyl chloride (FCl, HOCI,
NH,CI, CH,Cl) have been made and compared with the experimentally
determined values.
In many cases the theoretical investigations are carried out in an attempt to
facilitate the interpretation of either or both U.V. photoelectron spectra
(U.P.S.)132-134and X-ray absorption and emission spectra.132Two assign< n < 3) have been
ments of the U.P.S. of the chloromethanes CH,CI,,(O
r e p ~ r t e d . l ~Using
~ * l ~extended Hiickel MO calculation^,^^^ the current symmetry assignments of the ionized states of CH3Cl and CCI, are confirmed,
whereas revisions are suggested for those of CHCI, and CH,Cl,. On the other
hand, the results of CND0/2 calculations1= lead to assignments for the nonbonding orbitals which are different to those previously reported. In general,
however, the calculated ionization energies1,, are in good agreement with
available experimental data132*133
(Table 9). The U.P.S. of tetrafluoromethane
Table 9 Experimentaland calculated ionization energieslev of methyl chloride
Calculated133
Asslgnrnent Experirnei~taP~~~~~~
(CND0/2)
2e
3a1
le
2a1
11.3
14.4
15.4
21.5
11.40
13.75
16.56
21.59
and those of the analogous silicon and germanium molecules have been
determined using a double-focussing electron ~pectr0meter.l~~
With the aid of
CND0/2, MINDO, and SCCMO semi-empirical calculations, the ionization
131
132
133
W. G. Alcock, E. J. Hayward, B. Mile, and B. Ward, Canad. J. Chem., 1972,50,38 1 3 .

G. L. Bendazzoli, D. G. Lister, and P. Palmieri, J.C.S. Faruday 11, 1973, 49, 791.
F. Hopfgarten and R. Manne, J . Electron Spectroscopy, 1973, 2 , 13.
S. Katsumata and K. Kimura, Bull. Chem. SOC.Japan, 1973, 46, 1342.
A. E. Jonas, G. K. Schweitler, F. A. Grimm, and T. A. Carlson, J . Electron Spectroscopy, 1972, 1 , 29.
246

energies have been assigned to specific valence-level molecular orbitals. Two
other papers have been published which describe the photoelectron spectra of
ha loge no me thane^.^^^^^^ The U.V. photoelectron spectra of the fluorochloromethanes CF3Cl, CF,HCl, CFH,Cl, CFHCl,, CF,CI,, and CFCl, and the
fluorobromomethane CF,Br have been r e ~ 0 r t e d . lThe
~ ~ resonance photoelectron spectrum of methyl iodide has also been obtained by exciting individual auto-ionizing Rydberg states and measuring the ejected electron energies
by a time-of-flight technique.136
The carbon K, chlorine Kp, and chlorine L11.111X-ray emission spectra of
the chloromethanes CH,Cl,-, (0 < n Q 3),132the corresponding carbon and
fluorine K, spectra of the fluoromethanes CH,F,,
(0 Q n Q 4),13' and the
fluorine K absorption spectra of the flu~romethanesl~~
have been determined.
The spectra of the fluor~methanesl~~
are said to complement recently obtained
high-resolution U.P.S. of these molecules; the chloromethane spectral3, are
interpreted with the aid of the results of a theoretical analysis of their electronic structures.
The vacuum-u.v. absorption spectra of the fluoromethanes CHnF4-,
(0 < n Q 3),138 the chloromethanes CH,C14-, (0 Q n Q 3),139 the fluorochloromethanes CF3Cl, CF,HCl, CFH,Cl, CFHCI,, CF,C12, and CFC13,135
and the fluorobromomethane CF3Br 135 have been reported and discussed.
and the mixed ha10genomethane.s~~~
The spectra of the chlor~methanesl~~
are compared with the corresponding U.P.S. ; although certain analogies are
readily seen, it is thought that the full relationship between the two spectroscopic techniques is not entirely understood at present. The spectra of the
fluoromethanesls8 are compared with previously published electron-impact
spectra and are found to be quite similar. The results of a recent study of the
electron-impact spectra of the fluoromethanes CH,F4-, (0 Q n < 4) have
also been described in two communications.140J41
Several analyses of high-resolution gas-phase i.r. and Raman spectra of
methyl halides, including those of CH3F,142CHD2C1,143CH3Br,lU and
CH31,145-147have been undertaken. The ground-state molecular geometry of
J. Doucet, P. Sauvageau, and C. Sandorfy, J. Chem. Phys., 1973, 58, 3708.
T. Baer and B. P. Tsai, J . Electron Spectroscopy, 1973,2,25.
lS7 R. E. Lavilla, J. Chem. Phys., 1973, 58, 3841.
la' P. Sauvageau, R. Gilbert, P. P. Berlow, and C. Sandorfy, J. Chem. Phys., 1973, 59,
762.
lag B. R. Russell, L. 0. Edwards, and J. W. Raymonda, J. Amer. Chem. SOC.,1973,95,
21 29.
140 W. R. Harshbarger and E. N. Lassettre, J. Chem. Phys., 1973, 58, 1505.
W. R. Harshbarger, H. B. Robin, and E. N. Lassettre, J. Electron Spectroscopy,
1973, 1, 319.
lPaM. Betrencourt, J. Mol. Spectroscopy, 1973, 47, 275.
lL3 J. L. Duncan, D. C. McKean, P. D. Mallinson, and R. D. McCullough, J. MoZ.
Spectroscopy, 1973, 46, 232.
144 C. Betrencourt-Stirnemann and M. Morillon-Chapey, J. Mol. Spectroscopy, 1973,
46, 171.
145 H . Matsuura and J. Overend, Bull. Chem. Sac. Japan, 1973, 46, 1102.
146 H. Matsuura, T. Nakagawa, and J. Overend, J. Chem. Phys., 1973,59, 1449.
14' M. Constant and R. Fauquembergue, J . Chem. Phys., 1973,58,4030.
135
247
methyl chloride and its deuteriated analogues has been fixedlg3as

r(C-H)
r(C-D)
r(C-Cl)
= 1.090 f 0.002 A
= 1.088 f 0.00219
= 1.7854 f 0.0010 A
and LWCH = 110'45' from the analysis of the i.r. spectra of CHD,Cl by
assuming that zero-point energy effects a shortening of the C-H bond length
The use of the CH stretching frequency in
by 0.00219 on de~teriati0n.l~~
CHD,-substituted methyl compounds, together with the knowledge of a
single unperturbed CH, stretching frequency, is proposed as an approximate
method for estimating the positions of CH, stretching bands, affected by
Fermi resonances, involving CH, deformation overtones and corn bin at ion^.^^^
With additional assumptions the positions of CD, stretching modes can also
be predicted. Predictions of the unperturbed positions of vcH(sym) have been
made for, inter alia, the four methyl halides.
The i.r. spectra of CH,F2,149CD,F2,14gCH,CI,,150 CIF,,151 and CIC13151*152
have been measured under high resolution; the Raman spectra of CIC1252
and, inter alia, CF4l6, and CCl,153 have also been recorded in the vapour
phase. The spectra of the tetrahalogenomethanes were determined at 20 and
141) "C, re~pective1y.l~~
The i.r. and Raman spectra of CIC1,152 have been
interpreted in terms of CICI, fundamentals together with additional bands
assigned to CICls decomposition products (C,CI, and I,) and a secondary
contaminant (CCI,).
A number of halogenomethanes have been subjected to other forms of
molecular s p e c t r o ~ c o p y ?High-resolution
~~~~
Stark spectra of several
transitions of the v, band of CH,F have been studied by means of a CO,
laser;154 measurements of the hyperfine structure on certain rotational
transitions in CH2F2have been made using a molecular beam maser spectrometer ;155 the millimetre-wave spectrum of ground-state CDC1,156 and the
microwave spectrum of CD31 in excited vibrational states have also been
observed.
The application of molecular spectroscopic techniques to an elucidation of
molecular reorientations and interactions of halogenomethanes in the liquid
phase has been described. The usefulness of Raman spectroscopy in probing
the details of molecular motion in liquids has been demonstrated for
D.C.McKean, Spectrochim. Acta, 1973, 29A, 1559.
I. Suzuki and T. Shimanouchi, J. Mol. Spectroscopy, 1973, 46, 130.
P. C. M. Van Woerkom, J. de Bleyser, and J. C. Leyte, Chern. Phys. Letters, 1973, 20,
592.
151 A. I. Baise, J.C.S. Faraday II, 1972, 68, 1904.
15a R. H. Mann and P. M. Manis, J. Mol. Spectroscopy, 1973, 45, 65.
lK3
R. J. H. Clark and D. M. Rippon, J. Mol. Spectroscopy, 1972, 44,479.
lb4F. Herlemont, J. Lemaire, J. Houriez, and J. Thibault, Compt. rend., 1973, 276, B,
733.
166 S. G. Kukaich, J. H. S. Wang, and D. J. Ruben, J . Chem. Phys., 1973, 58, 5474.
150 D. B. McLay and G. Winnewisser, J . Mol. Spectroscopy, 1972, 44, 32.
lb7R. L. Kuczkowski, J. Mol. Spectroscopy, 1973, 45, 261.
14*
14*
160
248
CH31,158-1ao CD3I7160 CH3Br,le1and CDC13.1G1Analogous n.m.r. relaxation

studies have been carried out on liquid CH3115 and CC1,F.162The analysis of
far4.r. spectra has also been applied to the problem of reorientational motions
of the liquid halogenomethanes CHF3,163CF4,164CBr4,164and CI,.164 In
particular, the analysis of the Raman and n.m.r. spectra of CH31159give an
activation energy of reorientation perpendicular to the C3axis of the molecule
of 2.1 kcal mol-l and an activation energy for reorientation about the C3axis
of 0.4 kcal mol-l, indicating quasi-free rotation for this molecule. On the
other hand, the results of the far-i.r. analysis of molecular motion in liquid
CHF3 indicate that there is essentially free rotation.
Experimental measurements in dilute solutions have been made of the i.r.
and Raman spectra of a range of compounds containing CH3X groups,
including CH3F, CH3Cl, CH,Br, and cH31?65Attention is focussed on the
regions of vCHs stretching fundamentals (3000-2700 cm-l) and the QCHt
internal angle-bending fundamentals (1500-I 200 cm-I), with particular
reference to addition absorptions in the vCH3 region which originate in overtone transitions of dCHs fundamentals. In a separate investigation of the
Raman spectra of solutions of CH31and CD,I in CS2 solution,160the fundamental bands have been studied to obtain information about molecular
rotational and vibrational dynamics.
The crystal structures of CH,BrlG6and C H 3 P have been determined by
Kawaguchi using X-ray diffraction methods at approximately - 120 and
-80 OC, respectively. The crystals are isomorphous, with an orthorhombic
space group D&-Pnma.The unit-cell parameters are given in Table 10.
Table 10 Unit-cellparameters/A for methyl bromide and methyl iodide:
2=4
Compound
CH,Br
CHJ
4.47
4.59
6.42
6.98
9.15
10.11
These structures are quite different from that of methyl chloride, which
has symmetry C & - - - C ~ CIn~ all
~ . three crystals, all the molecules lie on the
mirror planes, the difference lying in the mutual orientations of the molecules.166Kawaguchi and co-workers have also reported the results of X-ray
R. B. Wright, M. Schartz, and C. H. Wang, J . Chem. Phys., 1973,58, 5125.
J. E. Griffiths, Chem. Phys. Letters, 1973, 21, 354.
H. S. Goldberg and P. S. Pershaw, J . Chem. Phys., 1973, 58, 3816.
161 I. Laulicht and S. Meirman, J . Chem. Phys., 1973, 59,2521.
162 K. T. Gillen, D. C. Douglass, M. S. Malmberg, and A. A. Maryott, J. Chem. Phys.,
1972, 57, 5170.
163 A. I. Bake, J.C.S. Faraday II, 1972, 68, 1904.
164 K. M. Ewool and H. L. Strauss, J. Chem. Phys., 1973, 58, 5835.
165 J. C. Lavalley and N. Sheppard, Spectrochim. Acta, 1972, 28A, 2091.
166 T. Kawaguchi, M. Hijikigawa, Y. Hayafuji, M. Ikeda, R. Fukushima, and Y. Tomiie,
Bull. Chem. SOC.Japan, 1973, 46, 53.
15*
15s
lG0
249
diffraction investigations of the structures of CH2C12,1G7
CH,Br2,168 and
CH2121G8
at approximately -120, -90, and -20 'C, respectively. Whereas
the structure of the dichloro-compound has orthorhombic symmetry DiiP b c r ~those
, ~ ~ ~of the dibromo- and di-iodo-compounds, which are isomorphous, have monoclinic symmetry C&-C21 c.168 The unit-cell parameters for
all three molecules are given in Table 11. It is noticeable that the contribution
Table 11 Unit-cell parameters for dichloro-, dibromo-, and di-iodo-methane
alA
CHzCla
CH,Br,
CHJP
CIA
bIA
4.249 8.138
12.239 4.459
13.346 4.720
9.492
15.212
16.479
PI"
113.54
114.48
Z
4
8
8
Ref.
167
168
168
of the dipole-dipole interaction in the crystal of dichloromethane is much

larger than that in the crystals of dibromo- and di-iodo-methane. This suggests
that dipole-dipole interactions play an important role upon solidification,
leading to a crystal structure for CH2CI, different from those of CH2Br2
and CH212.1G7
The crystal structures of the low-temperature (<76.2 K) a-CF4 phase169
and two high-pressure polymorphs of CCI, have been reported. The crystal
data for a-CF, at 10K show it to have a monoclinic structure with space
group P2Jc; the unit-cell parameters are given in Table 12.169The crystal and
Table 12 Unit-cell parameters for tetrafuoro- and tetrachloro-methane
alA
blA
CIA
Bl
Z Ref.
O
E-CF,
CCI, (111)
8.435 f 0.005
9.079 f 0.012
4.320 f 0.002
5.764 f 0.003
8.369 f 0.005
9.201 f 0.004
119.40 f 0.05
104.29 f 0.05
4
4
169
170
molecular structures of a high-pressure modification of carbon tetrachloride

(CCI, 111) were determined at approximately 10 kbar pressure;17oit crystallizes with monoclinic symmetry with the unit-cell parameters given in Table 12.
Observed i.r. spectra indicate that the CCI, molecule exhibits regular tetrahedral symmetry at 10 kbar.170 A more compact phase than CCI, I11 was
predicted in the CCI, system on the basis of packing efficiency and the phase
CCl, IV was subsequentlyverified by visual observation in microscopic studies
at pressures in the 35-40 kbar range and temperatures up to 500 OC.170
The i.r. spectra of solid CHC13:71 CHI,,172 and CD13,172and the Raman
spectra of solid CHC13,173CDC13,173CHI3 9172 CD13,172and CH3F174have been
T. Kawaguchi, K. Tawaka, T. Takeuchi, and T. Watanabe, Bull. Chem. SOC.Japan,
1973, 46, 62.
T. Kawaguchi, A. Wakabayashi, M. Matsumoto, T. Takeuchi, and T. Watanabe,
Bull. Cltem. SOC.Japan, 1973, 46, 57.
Itlo D. N. Bol'shutkin, V. M. Gasan, A. I. Prokhvatilov, and A. I. Erenburg, Acfu Cryst.,
1972, B28, 3542.
170 G.J. Piermarini and A. B. Braun, J. Chem. Phys., 1973, 58, 1974.
171 E.A. D'Alesio, E. Dodero, and C. Pomposiello, J. Chem. Phys., 1972,57,4136.
172 N. Neto, 0. Dehler, and R. M. Herter, J. Chem. Phys., 1973, 58, 5661.
H. F. Shurvell, J. Chern. Phys., 1973, 58, 5807.
A. J. Barnes, H. E. Hallam, J. D. R. Howells, and G. F. Scrimshaw, J.C.S. Faraday
II, 1973, 69, 738.
16'
250

recorded at low temperatures; the assignments of the vibrations of the
crystalline molecules are consistent with their crystal structures.171J73
The vibration-rotation spectra of matrix-isolated CC1417s and the halogenomethanes CH3X (X = F, C1, Br, or I)174have been reported. The Raman
matrix spectrum of CCI, (dilution 1 :400 to 1 :600) has been recorded using a
Cary Model 81 spectrophot~meter.~~~
The concentration dependence of the
i.r. spectra of the halogenomethanes isolated in argon matrices at 20 K has
been studied; the results show the growth of multimer bands, the predominant
species being a linear dimer:
a+
8-
HsC-F*
6+
* * *
*.
6-
*HIC-F
that is stabilized by attraction of the molecular dipoles. Discrete absorptions

due to larger multimers were also observed in the C-X stretching region.174
No evidence was found for the rotation of CH,F in either argon or methane
matrices.175
Many of the chemical reactions of halogenomethanes that have been
described during the period of this Report involve their interaction with
atomic species, particularly the s-electron element metals and the halogens.
Molecular beam reactions of potassium with CH3117'and CC14,177of barium178
with CH,I, CH212,CFJ, and CCl,, and of strontium178and calcium178with
CH31and CH212have been described. Codeposition of halogenomethanes and
alkali metals in low-temperature inert-gas matrices gives rise to matrix-isolated free radicals. From a study of the e.s.r. spectra of matrix-isolated CCl,
radicals, produced by the reaction of lithium with carbon tetra~hloride,~'~
it has been possible to show that the species is pyramidal with an angle of
15.5' f 2' between the C-CI bonds and a plane perpendicular to the C3
axis; this corresponds to a ClCCl angle of 113' f 2'. Codeposition of CH212
with lithium, sodium, or potassium atoms in an argon matrix produces new
i.r. bands which are attributable to the CHJ free radical.lsOThe assignment
of the spectra is supported by vibrational analysis, the high C-I force constant (2.81 f 0.04 mdyn A-1) indicating the presence of .rr-bonding in .CH21.
Several papers have been published describing the reactions of halogenomethanes with halogens; the systems which have been investigated are
summarized in Table 13,1s1-1s4 The kinetics and mechanism of the reaction
of atomic fluorine with CF31and CC1,Br have been investigated in a fast-flow
reactor.ls2 The analysis of the results proves conclusively that both reactions
175
l'13
177
178
170
1. W.Levin and W. C. Harris, J . Chem. Phys., 1972, 57, 2715.

A. M. Rulis and R. B. Bernstein, J. Chem. Phys., 1972, 57, 5497.
T. M. Sloane, S. Y. Tang, and J. Ross, J. Chem. Phys., 1972.57, 2745.
S.-M. Lin, C. A. Mims, and R. R. Herm, J. Phys. Chem., 1973,77, 569.
G. Maass, A. K. Maltsev, and J. L. Margrave, J. Inorg. Nuclear Chem., 1973, 35,
1945.
D.W.Smith and L. Andrews, J. Chem. Phys., 1973, 58, 5222.

181 J. W.Bozzelli and M. Kaufman, J. Phys. Chem., 1973,77, 1748.
180
H. W. Chang and D. W. Setzer, J. Chem. Phys., 1973,58,2298.

M.A. A. Clyne and R. F. Walker, J.C.S. Faraday I, 1973, 69, 1547.
lE4
Z. B. Alfassi, S. Amiel, and M. Baer, J. Chem. Phys., 1972, 57, 3519.
182
lE3
251
Table 13 Summary of reactions of halogenomethanes with halogen atoms

Halogen
F
c1
Br
Halogenomethanes
CF31,1s1 CC1,Br,lsl CH3C1,1E2 CH2C12,1E2CHC13,182CH3Br1*2
CH,C1,lS3 CH2Clz,183 CHC13,1a3 CDCl,,183 CC13B1-lS3
CH3Br184
proceed primarily by abstraction rather than displacement of a halogen atom:
A similar conclusion is derived from an i.r. analysis of the excited HF product

of the abstraction reaction between fluorine atoms and CH,Cl, CH,Cl,,
CHCI,, and CH,Br.ls2 A complementary investigation of substituent effects
and stereochemical mechanisms for substitution reactions of lSFfor halogens
in, inter a h , CF,X and CH,X (X = F, C1, Br, or I) has been undertaken.ls5
Although no thermal substitutions of 18F for X are observed with CF,X
substrates in excess SF,, the corresponding substitution of lSFfor X in CH,X
molecules is thought to occur by an insertion mechanism, the yield increasing
as X is varied from fluorine to iodine.ls6
The kinetics of the reactions of chlorine atoms with a series of halogenomethanes have been investigated using mass-spectrometric techniques.ls3
The reactions of hot 80Br,produced by an (n, y ) reaction with CH,Br, were
studied in the presence of helium and krypton as moderators;ls4 the results
obtained were compared with those previously established for the formally
analogous reaction between hot 38Cl and CH,Cl.
In a similar investigation, the interactions of the halogenomethanes
CF,H, CH,F, and CH,C1 with molecular iodine excited with 185 nm radiation
have been studied in an attempt to elucidate the mechanisms of reactions of
excited iodine molecules.lss
A kinetic study of the reaction between dichloromethane and atomic
oxygen, produced by microwave discharge in oxygen diluted with helium,
has been undertaken.lS7The reaction products, detected by mass spectrometry, differ with the relative amounts of the reactants. In excess dichloromethane, the products are CO, HCl, H,, and COCl,; with excess oxygen
atoms, Cl,, H,O, and ClOH are found in addition to the other products.lS7
Comprehensive investigations of the radiolysis of the liquid fluoromethanes
CH,F4-, (0 < n 4 3)lS8and gas-phase mixtures of CF, and CCl4lSshave
been carried out. The radiolysis of the liquid fluoromethanes188was undertaken in an attempt to assess the effect that the structure of the molecules has
R. S. Iyer and F. S. Rowland, Chem. Phys. Letters, 1973, 21, 346.
C. Glasgow and J. E. Willard, J . Phys. Chem., 1973, 77, 1585.
lS7 J. Barassin and J. Combourieu, Bull. SOC.chim. France, 1973, 2173.
IE8
M. G. Robinson and G. R. Freeman, Canad. J . Chem., 1973, 51, 1010.
lE9
R. E. Marcotte and R. J. Hanrahan, J. Phys. Chem., 1972,76, 3734.
lS5
l E 6L.
252
on electron behaviour in liquid hydrocarbons. The main products of the gasphase 7-radiolysis of CF4-CCI, mixtures, which has been investigated as a
function of mixture composition, total dose, and effect of added oxygen
scavenger on product yields at 88 "C and total pressure of 920 Torr, are the
three possible chlorofluoromethanes CCl,F, CCl,F2, and CC1F,;lsg other
significant products are C,C16 and C,C14, with minor products including
C2F6, C,F,CI,, C,F4CI2, C,F,CI, and CI,. Small amounts of oxygen were
observed to scavenge between 90 and 100% of the products in equimolar
CF4-CCI, mixtures; it was thus concluded that the final products result
almost completely from free-radical processes under these conditions. At
conditions of maximum yield (6.2 mole % CCl,), however, oxygen scavenging
is only 70% effective, and a substantial contribution of ionic processes to the
final product yields is suggested.lsg
Three reports have been published describing the results of experiments
involving the photolysis of halogen~methanes.~~~-~~~
The absorption spectra
and decay times of transient species produced by laser flash photolysis of
solutions of CHI, in aromatic solvents have been reported;lS0 the results
indicate that the primary photolysis product is atomic iodine. Gaseous methyl
radicals were produced through flash photolysis of CH,I in order to obtain
and examine a portion of the i.r. spectrum of the methyl radical (450-740
cm-l) using a rapid-scan i.r. spectrometer.lgl The frequencies recorded for
CH,, CH,D, and CD, (Table 14) are close to the corresponding frequencies
Table 14 I.r. spectra (450-740
cm-l) of CH,, CH,D, and CD,
Radical
CHs
CH2D
CDs
Wavenumberlcm-l
607
561.2
460.6
603.3
558
457
for the matrix-isolated compound, which permits their assignment to v2,

the out-of-plane (umbrella) mode of CH3.1Q1An i.r. matrix-isolation study of
the products of the vacuum-u.v. photolysis of CHCIF, and CHC1,F has
shown the presence of the CCIF, and CC1,F free radicals in the low-temperature argon and nitrogen matrices.'93 Support for the identification of these
species has been obtained from studies of vacuum-u.v. photolysis of CDCIF,,
CDCl,F, and l3CHC1,F as well as from studies of halogen-atom abstraction
from CClF, and from CC1,F by sodium atoms in an argon matrix environment.lg2
The thermal decomposition of CC1,Br has been studied in the gas phase by
electron-diffraction techniques.lg3 Three different diffraction patterns were
A. Van Den Ende, S. Kimel, and S. Speiser, Chem. Phys. Letters, 1973, 21, 133.
L. Y. Tan, A. M. Winer, and G. C. Pimentel, J . Chem. Phys., 1972,57,4028.
lg2
D. E. Milligan, M. E. Jacox, and J. H. McAuley, J. Mol. Spectroscopy, 1973, 45,
377.
lQ3 T. L. Leggett and D. A. Kohl, J . Chem. Phys., 1973,59, 611.
lQo
lgl
253
recorded and analysed. For each of these patterns the major components in
the scattering volume were found to be mixtures of BrCC1,-BrCC12-CC1,eel,, c&1&2c16, and BrC1-Br,. With the exception of the C-Br bond,
which appeared to be abnormally large, all distances and angles had normal
values. A plausible explanation of the lengthening (0.15A) of the C-Br
bond is that a long-lived excited state of BrCC1,-BrCCl, was formed in the
react ion.lg3
The formation of complexes containing halogenomethaneshas been studied
by several groups of a ~ t h o r s . ~Solid-liquid
~ ~ - ~ ~ ~phase diagrams have been
obtained from thermal analysis and d.t.a. for the three binary systems
dimethyl sulphoxide (DMSO)-CHC1,,194 DMSO-CC14,1s4 and TeC14-CC1,.195
Whereas the DMSO-CHCI, system forms both a stable and metastable
addition compound, the empirical formula for both compounds being
DMSO,(CHCl,),, both systems involving CCl, are simple eutectics with no
evidence for solid compounds.194~1g5
The presence and absence of compounds
in the DMSO-CHCl, and DMSO-CCl, systems is stated to be in qualitative
agreement with the concept that the bonding in the compounds formed is
based on hydrogen bonds formed between oxygen of DMSO and a hydrogen
atom of the ha10genomethane.l~~
The results of an investigation of the molar
excess enthalpy of the system CC1,-MqN are consistent with complex
formation between unlike molecules and are thought to provide further
evidence for the electron-acceptor ability of cc14?Q6
A second example of the
complexing ability of CClaS7has been obtained from a Raman-spectroscopic
investigation of solutions containing tetra-alkylammonium chlorides or
bromides and CCl, or CBr, in non-hydrogen-bonding solvents. The spectra
give direct evidence of 1 :1 complexes X-CBr, present in ion pairs with the
cation. Evidence is also presented showing that in CBr,Cl- the C1- ion is
bound to a face rather than an apex or edge of the CBr, tetrahedron.lg7
The low-frequency Raman spectra of a series of solid mixtures of benzene
and carbon tetrachloride have been measured at 80K.lg8 They have been
rationalized by comparison with the Raman spectra of the pure components;
thus the mixtures are thought to consist of two distinct crystalline phases C6H6 and C6H6,2CCl, - the latter being a charge-transfer complex with a
very weak C6H6-cC1, force constant (0.27 mdyn A-1).
In two communications, a group of Russian workers have summarized the
enthalpies of formation1ggand bond-rupture energies200of all the halogenomethanes. These parameters are studied in relation to the number and type
J. R. Groates, J. B. Ott, J. Reeder, and J. D. Lamb, J.C.S. Faraduy I , 1972,68,2171.
V. V. Safonov and A. V. Konov, Rum. J. Inorg. Chem., 1972,17, 1766.
lg6 D. V. Fenby, Austral. J. Chem., 1973, 26, 1143.
lS7 J. A. Creighton and K. M. Thomas, J.C.S. Dalton, 1972, 2254.
lg8 J.-P. Viennot and G. G. Dumas, Compt. rend., 1972, 275, B, 489.
lgB
Yu. G . Papulov, L.V. Chulkova, V. P. Levin, and A. E. Stepanyan, J. Struct. Chern.,
1972,13, 655
loo Yu. G. Papulov, L. V. Chulkova, V. P. Levin, and A. E. Stepanyan, J. Struct. Chem.,
1972,13,895.
lg4
lg6
254

of substituents involved; within the limits of the adopted scale, the relationships are linear and the lines corresponding to the introduction of any particular substituent (F, CI, Br, or I) are parallel. A detailed analysisZo1of the
thermodynamics of the equilibrium:
Br,
+ CH +
Br
+ CH,Br
which has been studied in the temperature range 347-477 O C , has led to a
determination of the dissociation energy of the CH,-Br bond [D(CH,-Br)
= 293 kJ mol-l] and of the enthalpy of formation [AH;(CH,Br) = -34.3 f
0.8 kJ mol-l] of the CH,Br molecule.201
Other Substituted Methanes. The structures of several methane derivatives
have been determined by a variety of techniques.22-206From an analysis of
the microwave spectra of ground-state and excited torsional states of a
number of isotopic species of CH,SeH (l), the structural parameters of this
molecule have been derived.202The methyl group is tilted 1.5" away from the
C-Se internuclear line; the dipole moment of the molecule is ,u = 1.291 D
and the barrier hindering internal torsion has been calculated to be 1.001
kcal mo1-1.202 The structure of aminoacetonitrile, NH2CH2CN, has also
been determined from an analysis of its microwave spectra;203in this case
the three isotopic species NH,CH,CN, NHDCH,CN, and ND,CH,CN were
studied. The onlv rotamer observed is the form in which the two NH bonds
are gauche to the CN group (2) and the structure (3) is quite rigid; the
.
I
(2) X = CN.
(3) *assumed
rigidity of the molecule and its preference for the form in which the aminoprotons are closest to the triple bond confirms an earlier suggestion that there
is a strong hydrogen-bonding interaction between the amino- and nitrile
ao2
203
204
206
206
K. C. Ferguson, E. N. Okafo, and E. Whittle, J.C.S. Furuday I, 1973, 69,295.

C. H. Thomas, J . Chern. Phys., 1973,59,70.
H.M. Pickett, J. Mol. Spectroscopy, 1973,46, 335.
N. I. Sadna, L. V. Vilkov, and T. M. Anfimova, J . Struct. Chern., 1972, 13, 717.
F. N. Masri, J. L. Duncan, and G. K. Speirs, J . Mol. Spectroscopy, 1973,47, 163.
K.Rubin and R. Rudman, J. Phys. Chem., 1972,76,3973.
255
An electron-diffraction investigation of the molecule ClCH,NO,

(4) has been undertaken in the gas phase?" The structural parameters
(4)
shown have been determined assuming r(C-H) = 1.095 A and LHCH =

111". The results also suggest that there is either free rotation about the
C-N bond or a slightly hindered rotation with potential energy less than
1 kcal m01-1.204 The molecular structure of CD,CN has been determined
from an analysis of its high-resolution vibration-rotation spectra;205the
results are consistent with a CD, group geometry r(C-D) = 1.096 f 0.004A
and L D C D = 108" 56' f'0 30', assuming r(C-N) = 1.1572A and
v(C-C) = 1.4582 A.
The crystal structure of tetracyanomethane, C(CN)4,206has been shown to
be monoclinic, with space group Cc or C2jc and structural parameters
u = 9.361(6), b = 8.851(5), c = 6.241(8)A; /3 = 91.30(6)". No crystallographic phase transitions were observed at normal pressures in a differential
scanning calorimetry study from -150 to +16OoC, which is the decomposition temperature of C(CN),.206
Considerable interest has recently been shown in the conformational and
rotational properties of simple molecules. Thus of the preceding five structural papers, part of the discussion of three of these described the barriers to
Several other
rotation of CH,SeH,202 NH,CH2CN,203and C1CH2N02.204
reports have been published which describe the rotational properties of some
of the substituted methane~.~O~-~O~
A theoretica1207 (LCAO-SCF-MO
calculations) and an experimenta1208(microwave spectroscopy) analysis of
HOCH2CN and DOCH2CN show that the molecules exist as the gaucherotamer (5a, 5b) in the gas phase. The derived rotational constants indicate
that the angle between the HOC and OCC planes at the potential minimum is
approximately 123" from the rruns-position ( ~ C ) . ~The
O ~ barrier to internal
& &
H
H
gauche
207
ao8
20*
gauche
X = CN
(5b)
H
trans
(54
(54
G. L. Bendazzoli, F. Bernardi, and P. Palmieri, J.C.S. Furuduy II, 1973, 69, 579.
G. Cazzoli, D. G. Lister, and A. M. Mirri, J.C.S. Faruday II, 1973, 69, 569.
D. R. Lide, D. R. Johnson, K. G. Sharp, and T. D. Coyle, J . Chem. Phys., 1972,57,
3699.
Inorganic Chemistry of the Maingroup Elenrmts
256
rotation of CF3SiF, has been determined to be 489 f 50 cm-l, correspcnding

to a torsional frequency of 37.0 f 2.0 cm-l from an analysis of its microwave
A number of other theoretical studies of the potential-energy
surfaces, internal-rotation barriers, and related molecular parameters of
CH,N0,210 CW3NH2,211CH30H,211 FCH20H,212 CH(N02)3213and its
halogenated derivatives CX(N02), (X = F, Cl, Br, or I),213and CH20H- 214
have been undertaken. The theoretically derived rotational barrier of nitrosomethane (1.16,1.06 kcal mol-l depending on the model adopted) is very close
to the experimentally determined value210(1.137 kcal mol-l). The calculations
also predict that the eclipsed conformation (6) is the more stable one.21o
The computed potential-energy curve for the ground state of FCH20H
shows a single minimum which corresponds to the conformation (7), in
which the polar CF and OH bonds are gauche.212 (cf. HOCH,CN and
DOCH,CN).
A theoretical study of the topomerization of CH20H- [ i e . the conformational transformation from one Y conformation (8) into another]andthe tautomerization of this species into the methoxide anion, CH,OHCH,O-,
has been effected.214The topomerization proceeds via the W conformation
(9) as an intermediate by two separate events, uiz. rotation about the C-0
bond with a barrier of 10.58 kcal mol-l and pyramidal inversion at carbon
210
A. R. Mochel, L. L. Griffin, R. W. Kramling, and J. E. Boggs, J. Chem. Phys., 1973

58,4040.
212
a13
214
M. S. Gordon and W. England, J. Amer. Chem. SOC.,1973, 95, 1753.

S. Wolfe, L. M. Tel, W. J. Haines, M. A. Robb, and I. G. Csizmadia, J . Amer. Chern.
SOC.,1973,95,4863.
M. I. Dakhis, A. A. Levin, and V. A. Shlyapochnikov,J. Struct. Chem., 1973,14,143.
S . Wolfe, L. M. Tel, and I. G. Csizmadia, Canad. J . Chern., 1973, 51, 2423.
257
with a barrier of 20.52 kcal mol-l. The major factor influencing the tautomerization is the extra stability of CH30- with respect to CH20H-. In its
ground electronicstate CH,O- is 22.18 kcal mol-l more stable than CH20H-;
in low-lying excited states, however, all conformations of CH20H- are
stabilized with respect to CH30-.214 A theoretical analysis of the isomerization
CH3NC -+ CH,CN has also been carried out, the principal object being the
interpretation of the transition state.216This particular tautomerism has also
been the subject of an investigation216in which experiments have been made to
assess the importance of radical chain effects in the thermally induced reaction.
It is concluded that there is no reason to doubt the fact that the isomerization
of methyl isocyanide is an excellent test for the theory of unimolecular
reactions.
The phenomenonof molecular reorientational motion in liquidCH,CN2170218
and CD3CN217has been investigated using i.r.217 and Raman spectroscopic
techniques. It was found to be possible to estimate the activation energy for
liquid-state molecular reorientations perpendicular to the C3 symmetry axis
as 2.0 f 0.3 kcal mol-l, which is in good agreement with existing n.m.r.
and microviscosity values.217
Detailed spectroscopicinvestigationsof gas-phase CH3CN,219*220
CD,CN,219
CF3CN,221CH3N0,220CH30N0,222and CD30N0,222solid-state CH36N,223
CD3CN,223CH30H,224and CD30H,224and matrix-isolated CH,0N0222and
CD,0N0222 have also been completed and the data theoretically analysed.
Surprisingly little information has been published describing the inorganic
chemistry of substituted methanes other than the halogenomethanes. The
largest section, however, concerns the reactions of methanol and methanethiol. The oxidation of methanol in the presence of V,0,-Cr,03 catalysts has
been
in an attempt to determine the effect of the catalyst composition on its activity and selectivity. The maximum selectivity with respect to
the formation of formaldehyde corresponds to 1-5 mole% Cr203 (the
region corresponding to the existence of a solid solution in the system.)
The catalytic interaction of CH,OH and HCI (for vapour-phase synthesis of
CH3Cl) has been studied226on catalysts of different chemical nature (zinc,
cadmium, mercuric, and bismuth chlorides deposited on active alumina).
The most active catalyst correlates with the maximum heat of adsorption of
215
216
217
218
21s
220
221
222
223
224
226
226
D. H. Liskow, C. F. Bender, and H. F. Schaefer, J. Chem. Phys., 1972, 57, 4509.

T. Fujimoto, F. M. Wang, and B. S. Rabinovitch, Canad. J. Chem., 1972, 50, 3251.
J. E. Griffiths, J . Chern. Phys., 1973, 59, 751.
M. Kakimoto and T. Fujiyama, Bull. Chem. SOC.Japan, 1972, 45, 3021.
S. G. Kukolich, D. J. Ruben, J. H. S. Wang, and J. R. Williams, J . Chem. Phys., 1973,
58, 3155.
R. Zahradnik and P. &wsky, Coll. Czech. Chem. Comm., 1973, 38, 1876.
S. J. Daunt and H. F. Shurvell, J. Chem. Phys., 1973, 58, 3532.
J. F. Ogilvie, J.C.S. Chem. Comm.,1973, 450.
M. P. Marzocchi and M. G . Migliorini, Spectrochim. Acta, 1973,29A, 1643.
S. K. Garg and D. W. Davidson, J. Chem. Phys., 1973, 58, 1898.
L. N. Kurina and 0. N. Ediseeva, Rum. J . Phys. Chem., 1972, 47, 333.
I. I. Kurlyandskaya, S. B. Grinberg, T. F. Kudryavtseva, E. B. Svetlanov, R. M. Flid,
and R. V. Dzhagatspanyan, Russ. J. Phys. Chem., 1973, 47, 101.
258
methanol at low surface coverage and the greatest fraction of the monolayer
covering of the carrier with the catalytic chloride.
1.r. studies of the products of the 14'70A photolysis of isotopically substituted methanols in argon and nitrogen matrices at 14 K have provided
evidence for the stabilization of a significant yield of CH20H.227From a
theoretical analysis of the i.r. data it has been possible to conclude that (i)
the C-0 bond of CH,OH is slightly stronger than in CH,OH, (ii) the torsional barrier is significantly greater than in CH,OH; both these findings are
in accord with earlier e.s.r. data.227
As part of a programme concerned with negative-ion formation at low
electron energies, the formation of negative ions by electron bombardment of
CH,OH, CH,OD, and CD,OH has been investigated228as a function of
electron energy; various ionization processes have been suggested to account
for ion formation.
The photochemistry of methanethi01~~~
at 254 and 214 nm as well as the
produced by photolysis
reaction of methanethiol with hot hydrogen
of HI at 300 nm, has been investigated. Quantum yields for the production
of hydrogen, methane, and dirnethyl disulphide in the photolysis of methanethiol have been measured.22gThe addition of n-butane reduces the yield of
CH, and increases the yield of H2; the observations have been interpreted in
terms of a mechanism involving reactions of hot hydrogen atoms.22g
The products of thegas-phase photolyses of b0thnitromethane,CH,N0,,2~~
and methyl nitrite, CH,0N0,232*2.13
have been established; photolysis of
CH,NO, at 550C2,1 gave rise to CH,ONO, H2C0, CH,NO, and NO as
major products whereas photolysis of C H 3 0 N 0 between 25 and 150C,
and NO-N2,232NO-C0,233
both alone232and in the presence of
NO-N0,,233and NO-0233 mixtures yielded H2C0, N 2 0 , H20, and (in the
presence of NO, or 0,) CH,ONO,.
Free radicals produced in an oriented solid of methyl isocyanate by
y-irradiation have been studied by e.s.r. at -196 to -100 0C.234The original
radical and trapped electron were recorded at -196 OC in the dark. The
original radical was assigned as *CH,NCO. This was converted
completely into a new radical on irradiation with visible light for 90 minutes.
The spectrum of this radical enabled it to be assigned the H2C=Na
structure. The e.s.r. pattern of C H 2 N C 0was restored when the temperature
was raised to -120 "C. The mutual conversion of the two radicals by visible
M. E. Jacox and D. E. Milligan, J. Mol. Spectroscopy, 1973,47, 148.
J. C. J. Thynne and P. W.Harland, Internat. J . MussSpectrometry IonPhys., 1973,11,
127.
L. Bridges and J. M. White, J. Phys. Chem., 1973, 77, 295.
230 L. Bridges and J. M. White, J. Chem. Phys., 1973, 59, 2148.
231 K. Honda, H. Mikuni, and M. Takahashi, BUN. Chem. SOC.
Japan, 1972, 4S, 3534.
2R2 H. A. Wiebe and J. Heicklen, J. Amer. Chem. SOC.,1973, 95, 1.
233 H. A. Wiebe, A. Villa, T. M. Mellman, and J. Heicklen, J. Amer. Chem. SOC.,1973,
95, 7.
234 M. Fujiwara, N. Tamura, and H. Hirai, Bull. CJteni. SOC.
Japan, 1973, 46, 701.
257
259
light and heatwas concluded to be a decomposition of CH,NCOintoCH,=N*
and CO and a recombination of these two moieties:234
*CH,NCO
hv
H,C=N*
+ CO
The enthalpy of formation of methyl cyanide, AH,"(CH,CN), has been

determined from the results of photon-impact studies of CH,CN under
vacuum-u.v. light235The value obtained, AWf"(CH,CN)2 59 f 4 kJ mol-l,
agrees with the values obtained recently by bomb calorimetry. The bond
dissociation energy Do(CH3-CN) Q 5.32 f 0.03 eV was also determined in
the course of this
The final section of this Section of the Report is associated with the derivatives of trifluoromethyl h y d r o p e r o ~ i d e . ~ ~The
~ - ~ ~new
~ compounds
CF,OOPOF, and CF30POF2 have been prepared236by the reaction of trifluoromethyl hydroperoxide CF,OOH with p-0x0-bis(phosphory1difluoride),
P203F4, and difluorophosphine-p-0x0-phosphoryldifluoride, P20,F4. The
i.r. and n.m.r. spectra, physical properties, and some chemical reactions are
reported for the new compounds.236New synthetic routes to bis(trifluor0methyl)bis(peroxy)carbonate (CF,OO),CO and trifluoromethyl fluoroformyl
peroxide CF,OOC(O)F, based on the catalytic disproportionation of bis(fluoroformyl) peroxide FC(O)OOC(O)F, have also been derived.237
The kinetics of the constituent reactions of the equilibrium:
CF3OOCF3
+ CFaOF + COFz
have been measured in the temperature range 480-580K.238 The results

have been interpreted in terms of the mechanism shown in equations (13)CF300CFB
kl
2CF30
ka
CFsO
+F
kB
CF30F
k6
(15). Activation energies of 46.2 and 45.0 kcal mol-l have been derived for
steps 1 and 6, respectively; these values lead to bond dissociation energies
D"(CH,O-OCH,) = 46.7 f 0.8 kcal mol-l and D"(CH30-F) = 44.5 f
0.8 kcal mol-l for the central 0-0 bond in bistrifluoromethyl peroxide
and the 0-F bond in trifluoromethyl hypofluorite, respectively.238
236
936
a37
238
a38
18
H. Okabe and V. H. Dibeler, J. Chem. Phys., 1973, 59,2430.

P. A. Bernstein and D. D. Desmarteau, J . Fluorine Chem., 1973, 2 , 315.
D. Pilipovich, C. J. Schack, and R. D. Wilson, Inorg. Chem., 1972, 11, 2531.
R. C. Kennedy and J. B. Levy, J. Phys. Chem., 1972, 76, 3480.
J. D. Witt, J. R. Durig, D. D. Desmarteau, and R. M. Hannaker, Inorg. Chem., 1973
12, 807.
260

The i.r. spectrum of solid CF,OOOCF, and the Raman spectra of gaseous,
liquid, and solid CF3000CF3have been measured in the fundamental reA new vibrational assignment is proposed in which the symmetric
0-0 stretch of the triatomic 0-0-0 bridge is located at 875 cm-l; this
value is very similar to the value of 890cm-l for the 0-0 stretch in
CF,00CF3 and indicates a similarity in the 0-0 bond order in the two
molecules.239
Formaldehyde and its Substituted Derivatives.-Formaldehyde, Thioformaldehyde, Carbonyl Halides, and ThiocarbonylHalides. Several high-resolution
although
spectroscopic studies of formaldehydehave been undertaken ;240-243
the majority are gas-phase investigation^,^^^^^^ the i.r. spectra of H2C0 and
D2C0 in argon and nitrogen matrices and the Raman spectra of H2C0 and
D,CO in argon and of H2C0 in nitrogen matrices have been reported as a
function of both temperature and matrix c~ncentration.~~,
Bands associated
with monomeric and dimeric species are observed; the dimer spectra indicate
intermolecular interaction through the carbonyl gr0ups,2~~
(cf. the formation
of CH3F dimers in argon matrices at 20 K175).
Ab initio calculations on complexes formed between lithium cations and
formaldehyde show that the most stable configuration is characterized by an
interaction of 43.2 kcal mol-l, C,, symmetry, and an oxygen-lithium distance
of r(Li-0) = 1.77 A?44 Detailed analysis of the electron-density function
gives proof of the electrostatic nature of the complex and shows extensive
mutual polarization.
The bonding, energetics, and geometry for the ground and several excited
states of thioformaldehyde have also been investigated by ab initio MO
~alculations.2~~
The calculated molecular parameters are in good agreement
with the microwave structural results246(Table 15). In contrast to formaldeTable 15 Structural parameters of thioforrnaldehyde
r(C-S)/A
calc. (ref. 245)
exptl. (ref. 246)
1.631
1.611
r(C-H)/A
1.090
1.092
LHCHI"
114.6
116.9
hyde itself, the 0- and .rr-bonds are predicted to be polarized in opposite

directions in thi~formaldehyde~~~
(Table 16). The millimetre-wave spectrum
of thioformaldehyde has been measured;247a set of rotational parameters
are presented, representing the best fit of all available data on the molecule.
240
241
242
243
244
245
246
247
R. E. Bruns and W. B. Pearson, J . Chem. Phys., 1973, 58,2585.

F. W. Birss, R. Y. Dong, and D. A. Ramsay, Chem. Phys. Letters, 1973, 18, 11.
R. A. Toth, J . Mol. Spectroscopy, 1973, 46, 470.
H. Khoshkhoo and E. R. Nixon, Spectrochim. Acta, 1973, 29A, 603.
P. Russegger and P. Schuster, Chem. Phys. Letters, 1973, 19, 254.
N. C. Baird and J. R. Swenson, J . Phys. Chem., 1973, 77, 277.
D. R. Johnson, F. X. Powell, and W. H. Kirchhoff, J. Mol. Spectroscopy, 1971, 39,
136.
Y . Beers, G. P. Klein, W. H. Kirchhoff, and D. R. Johnson, J . Mol. Spectroscopy,
1972,44, 553.
261
Table 16 Comparison of populrrtioti analysis and calculuted d@ole moment for
H,CO and H,CS
C net charge
X net charge
H net charge
C n-orbital population
X .rr-orbitalpopulation
C-X n-overlap population
C-X o-overlap population
C-H overlap population
Calculated dipole moment/D
H2CO
HSCS
+0.192
-0.168
-0.122
+0.010
-0.012
0.952
$0.056
0.908
1.048
0.41 62
0.5079
0.7251
1.46
1.105
0.4070
0.5521
0.7558
1.58
Theoretical analysis of the vibrational spectra248of F,CQ, Cl,CO, and

Br,CO and the electronic spectra249of (CN),CO has been attempted; the
hyperfine structure on certain rotational transitions in F,CO has been observed using a molecular beam maser spectrometer.25o
Several spectroscopic investigations of the thiocarbonyl halides have been
carried o ~ t . The
~ ~U.V.
~ photoelectron
- ~ ~ ~
spectra (U.P.S.) of F2CS,251-253
C12CS:52-253 and FC1CS253have been determined using a He (I) source.
Many of the bands observed have associated vibrational structure which can
be correlated with known vibrational frequencies of the parent molecules.252
The ionization potentials have been assigned, on the basis of the vibrational
fine structures and the result of theoretical calculations, to molecular orbitals
which are connected with lone-pair electrons on the halogen or sulphur
atoms, the C-S n- and c ~ - o r b i t a l s . ~The
~ ~ -values
~ ~ ~ of some of these ionization potentials have been considered in relation to those of the corresponding
orbitals of carbonyl halides, H,CO, and H,CS. In general there is a decrease
in ionization in going from the thio-compounds to the simple ~ a r b o n y l s . ~ ~ ~
Detailed studies of the gas-phase electronic spectra of F,CS254and C12CS255
have been undertaken; a CNDO theoretical analysis of the vibrational
intensities of these two molecules has also been carried
A number of inorganic reactions involving both formaldehydeand carbonyl
fluoride have been reported during the period of this Report.257-263The
R. E. Bruns and R. K. Naik, J. Chem. Phys., 1973, 58, 1849.
C. H. Warren and C. Ching, Theor. Chim. Acta, 1973, 30, 1.
250 J. H. S. Wang and S. G. Kukolich, J . Amer. Chem. Soc., 1973, 95, 4138.
251 H. W. Kroto and R. J. Suffolk, Chem. Phys. Letters, 1972, 17, 213.
252 G. W. Mines, R. K. Thomas, and H. Thompson, Proc. Roy. Soc., 1973, A333, 171.
253 K. Wittez, A. Haas, and H. Bock, Chem. Ber., 1972, 105, 3865.
254 C. R. Lessard and D. C. Moule, Spectrochim. Acta, 1973, 29A, 1085.
255 E. R. Farnworth and G. W. King, J. Mol. Spectroscopy, 1973, 46, 419.
256 R. E. Bruns, J. Chem. Phys., 1973, 58, 1855.
257 P. S. Sankhla and R. N. Mehrotra, Indian J . Chem., 1972, 10, 1081.
258 G. P. R. Mack and 3. A. Thrush, J.C.S. Faraday I, 1973, 69,208.
259 H. P. Sperling and S. Toby, Canad. J. Chem., 1973, 51, 471.
260 E. S. Yeung and C. B. Moore, J. Chem. Phys., 1973,518, 3988.
861 S. G. Thomas and W. A. Guillory, J. Phys. Chem., 1973, 77, 2469.
2 6 2 D. E. Klimek and M. J. Berry, Chem. Phys. Letters, 1973, 20, 141.
263 R. C. Kennedy and G. H. Cady, J. Fluorine Chem., 1973, 3 , 41.
248
249
262
kinetics of the oxidation of H2C0 by oxygen atoms257and CeIV in acid

perchlorate solutions268have been investigated. The former reaction has been
studied in a flow system at 300 K using product analysis, e.p.r., and chemiluminescence;257an analysis of the results of the CeIV oxidation indicates
that the oxidation is effected by Ce(OH)3+in addition to Ce4+.258
A total of four examinations of the photochemistry of formaldehyde have
been d e s ~ r i b e d ? ~ ~A- -detailed
~~
analysis of the photochemical decomposition
of gaseous H,CO has been carried out over a wide range of experimental
conditions.259The proposed reaction mechanism, which gives reasonable
agreement with the experimental results, is basedonthetwo primary processes
(16) and (17) together with the secondary reactions (18)-(23). Predissocia-
2 He + .CHO
H,CO % H2 + CO
H2C0
HH.
+ H,CO H, + .CHO
+ *CHO + H2 + CO
3
2CHO --+ (CHO),

2*CHO 3 2CO
H2
CO
2CHO 3 HzCO
2H*(+ M) + Hz(+ M)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
(23)
tion, quenching, and energy transfer have been studied for single vibrational
levels of the first excited singlet state of H2C0 and D,CO as part of a wider
study of the photochemistry of H2C0.260
Photolysis experiments involving H2COF61D,C0,261 and HFC0262have
been carried out. U.V. and vacuum-u.v. photolysis of H,CO and D,CO in
argon, carbon monoxide, and carbon-monoxide-doped argon matrices have
been performed between 8 and 10 K.261The major products of the photolysis,
COYH,, HCO, and H, presumably arise from the two primary processes
(24) and (25) (cf. the photochemical decomposition of H2C0259).
H,CO
H,CO
% H. +
2 Hz +
.HCO
CO
The photolysis ( A > 1650A) of formyl fluoride, HFC0,262leads to HF i.r.

laser emission, the energy content of the HF photoelimination primary
product being only a small fraction (-7 %) of the available excess energy. It
was also observed that fluorine atoms may be formed as primary photochemical products.262
The reaction of carbonyl fluoride with fluorine:
F2C0
+ F2 -+
CF,OF
in the presence of various catalytic fluorides has been examined.263The

number of catalysts known to be active in this reaction has been enlarged to
include NaF, MgF,, CaFz, SrF,, BaF,, and LaF,. Silver fluoride, usually a
263
mixture of AgF2 and AgF, and thallium(rr1) fluoride have been found to
catalyse the reaction of F2C0 with F2 to give both CF,OF and CF,OOCF,,
the proportion of the latter increasing with decreasing temperature.262
Formic Acid and Formates. The vibrational spectra and the U.V. photoelectron
spectra (U.P.S.) of formic acid and its deuteriated analogues have been examined;264the character of the molecular orbitals from which the U.P.S.
bands originate is discussed in terms of the results of vibrational analyses and
MO calculations. CND0/2-MO-SCF calculations have been performed by
Rode for the mono-, di-, and tetra-solvates of Li+,265*266
Na+,265and Cl-,265*286
with formic acid. For the cations, long-range interaction is observed only with
carbonyl oxygen, while their most stable position is found to be between the
C-H hydrogen and carbonyl oxygen, confirming similar conclusions from
experimental results. In the case of anion solvation, however, considerable
interaction energy is found only for O-H hydrogen to chlorine distances
< 4 A accompanied by a simultaneous change in C-0 and O H bond
lengths, resulting from the formation of a hydrogen bond. Charge transfer
from chlorine to the solvent molecule, however, can be observed only for
short distances ( < 3 A).
The kinetics of the catalytic decomposition of formic acid on sodium tungsten bronzes Na,WO,, with x in the range 0 . 1 1 4 . 8 5 , and on tungstic oxide
have been investigated manometrically in a static system at 150-250 "C
with acid pressures of 25-30
The decomposition products were
CO,, CO, H20, and H,, the mole ratios C0,:CO and H2:C02being determined mass-spectrometrically.
The acid dissociation constant of the carboxyl radical C0,H (pK = 1.4)
has been determined from an analysis of the results of a pulse-radiolysis
study of aqueous solutions of formic acid and the formate anion.268
The kinetics of oxidation of the formate anion by aqueous bromine have
been investigated by a potentiometric method;269the product of the reaction
is CO,. The influence of y-irradiation on the kinetics of thermal decomposition
of lead formate has been asse~sed.2~~
The decomposition of the salt:
Pb(HC0O)a -+ PbO
+ H2CO + COZ
which occurs at 190 OC is enhanced considerably by prior irradiation of the

sample.
Two structural investigations of lithium formate monohydrate have been
~ n d e r t a k e n ~ ~inl .an
~ 'attempt
~
to fix the positions of the water protons. The
264
266
267
269
271
I. Watanabe, Y. Yokoyama, and S. Ikeda, Chem. Phys. Letters, 1973, 19, 406.
B. M. Rode, Chem. Phys. Letters, 1973, 20, 366.
B. M. Rode, J.C.S. Faraday ZZ, 1973, 69, 1439.
S. S. Moody and D. Taylor, J.C.S. Faraday I, 1973, 69,289.
G. V. Buxton and R. M. Sellers, J.C.S. Faraday I, 1973, 69, 555.
R. H. Smith, Austral. J. Chem., 1972, 25, 2503.
M. N. Ray and N. D. Sinnarkar, J. Inorg. Nuclear Chem., 1973, 35, 1373.
L. Muthukrishnan and J. Ramakrishna, Acta Cryst., 1973, B29, 375.
A. Enders-Beumer and S. Harkema, Acta Cryst., 1973, B29, 682.

264
results obtained from the lH n.m.r. investigation271and the single-crystal
X-ray diffraction data272are complementary; the crystal structure has been
determined to be orthorhombic with space group Pbn2, and unit-cell dimensions a = 6.483, b = 9.973, c = 4.847 A. The arrangement of some molecules
in the unit cell, showing the tetrahedral co-ordination of the lithium cation
(three formate oxygens and one water oxygen) and the water chain is depicted
in Figure l.272
Figure 1 Arrangement of mine molecules in the unit cell of lithium formate

monohydrate, showing the co-ordination of the lithium ion and the
water chain
(Reproduced by permission from Acta Cryst., 1973, B29, 682)
In a similar investigation the 2H n.m.r. spectra of strontium formate

[2EI,]dihydratehave been recorded27sat 29.5 "Cin an attempt to check which
of the two previously published structures of Sr(HC00),,2H20 is correct,
Unfortunately, the results are not consistent with the X-ray analysis of
Galign6 and F a l g ~ e i r e t t e s and
, ~ ~ ~only partially in agreement with that of
O ~ a k iIf. ~
~
the~ latter
structure is correct then the first formate ion appears
to be planar whereas the second one is bent out of plane by approximately
22O.
The Rarnan and i.r. spectra of copper formate tetrahydrate have been
recorded as a function of temperature.276The spectra at liquid-air temperatures do not show any obvious changes from those at ambient temperature,
even though the compound undergoes a phase transition at -38.9 'C.This is
explained as due to the fact that the frequency of reorientation of the protons
even in the low-temperaturephase is much less than the optical f r e q u e n c i e ~ . ~ ~ ~
274
275
M. Da GraCa Cravierinha Dillon and J. A. S. Smith, J.C.S. Faruduy 11, 1972, 68,
2183.
J.-L. GalignC and J. Falgueirettes, Compt. rend., 1961, 253, 994.
K. Osaki, Structure Reports, 1958, 22, 564.
R. S. Krishnan and P. S. Ramanujam, Spectrochim. Acta, 1972, 28A, 2227.
265
The hydrate Th(HCOO),,0.66H20 can exist at room temperature in two
polymorphic forms, L and I~l.2~~
The structure of the L modification is well
known; it is isomorphous with kTh(HCOO),. An analysis of the X-ray
diffraction data of single crystals and powders of the M form of Th(HCOO),,0.66H20 has shown that at room temperature the crystals are orthorhombic,
with space groupP2,2,2,, and the unit-cell parameters are a = 6.761 f 0.003,
b = 10.491 f 0.005, c = 12.323 f 0.005
The preparation of plutoniurn(II1) formate by the reaction of plutonium(n1) hydroxide with formic acid
has been rep0rted.2~ Characterization of the new compound has been
accomplished by analysis, t.g.a., X-ray powder diffraction, and i.r. spectroscopy; it was found to be formally analogous to the well-known lanthanide(II1)
formates in all its properties.
Derivatives of Group VI Elements.-Oxides, Sulphides, and Related Species.
Following the pattern adopted in the previous Report, these simple species
will be considered in order of increasing formal oxidation state. Carbon
suboxide, C 3 0 2 ,has been prepared by the reaction of chemically generated
carbon atoms with carbon monoxide:279
c + co 3 c=c=o
c=c=o + co --+ o=c=c=c=o
The far4.r. spectrum of gaseous C,0,280and the Raman spectra of both
gaseous2*0and solid C30280*281
have been recorded; the Raman spectra of
both crystalline phases of C302(solid-solid transition temperature -1 15 K)
were obtained and the results discussed with regard to a recently proposed
structure of the high-temperature crystal form of C302,which assumes a D2h
lattice with C 3 0 2molecules located on two sets of non-equivalent sites.
Surprisingly few basic theoretical and spectroscopic studies on carbon
monoxide and the analogous chalcogen derivatives have been carried out.
The electronic structures of inter aZia CO and CS have been studied by an
SCF-MO
The results for CO compare satisfactorily with those of
ab initio treatments; the electronic structure of CS suggests that this molecule
may complex with transition-metal ions to form thiocarbonyls. The highresolution U.V. photoelectron spectra of CS,283
produced in good yield either
by discharge or photolysis of CS2, and the emission spectrum of CS2**in
the vacuum- and near-u.v., obtained by microwave discharge in CS2, have
been obtained. The microwave spectrum of CSe has been 0bserved,2~~
leading
277
278
278
280
281
282
283
284
285
B. Mentzen and M. Prost, Compt. rend., 1973, 276, C , 229.

L. R. Crisler, J. Inorg. NucZear Chern., 1972, 34, 3263.
S. Kammula and P. B. Sheviin, J. Amer. Chern. SOC.,1973, 95, 4441.
L. A. Carreira, R. 0. Carter, J. R. Durig, R. C. Lord, and C . C . Milionis, J. Cizern.
Phys., 1973,59, 1028.
W. H. Smith and J. B. Bates, J. Raman Spectroscopy, 1973, 1, 83.
P. G. Perkins, Rev. Rouinaine Chim., 1973, 18, 1289.
D. C. Frost, S. T. Lee, and C. A. McDowell, Chern. Phys. Letters, 1972, 17, 153.
S. Bell, T. L. Ng, and C. Suggitt, J . Mol. Spectroscopy, 1972, 44,267.
J. McGurk, H. L. Tigelar, S. L. Rock, C. L. Norris, and W. H. Flygare, J. Chern.
Phys., 1973, 58, 1420.
266
to an internuclear distance of (1.67647 f 0.0002) x

cm. The molecule
was prepared by subjecting a mixture of CSe, and argon, to which a small
amount of CH,Cl, was added, to a discharge; the mechanism of CSe
production is described as:
disaharge
CSe, +--
discharge
CHaCl,+
-CHCl
+ Se ---+
+ 2Se
*CHCl + HC1
CSe + HCl
C
The i.r. absorption spectra of matrix-isolated CO (in argon at liquidhelium temperatures) have been recorded as a function of deposition conditions and recording temperatures.286Double-doping experiments have also
been carried out with H,O,NH,, and N,. The spectra were found to be extremely sensitive to experimental conditions, particularly to the presence of
impurities ; it was concluded that, in general, spectroscopic data associated
with matrix-isolated species must be carefully examined to avoid confusion
between absorption frequencies due to isolated solute molecules and those
due to solute molecules interacting with small impurities such as water.286
A detailed high-resolution i.r. study of specific vibrations of the borine
carbonyl species BH,-CO has been undertaken287in an attempt to further an
understanding of the bonding in the molecule.
Four investigations of the formation and reactions of excited CO have been
carried o ~ t ? ~Observations
~ - ~ ~ ~made on the production of vibrationally
excited CO by the reaction of oxygen atoms with simple hydrocarbons
(C2H2and CH,) have been used to clarify the mechanisms governing the
formation of CO in continuous-wave air-helium-hydrocarbon electrical
discharge lasers.288It is suggested that the discharge simultaneously dissociates 02,producing oxygen atoms, and the hydrocarbon, yielding fragments
such as CH2, CH, H, etc. Further reactions, such as (26)-(28), can then
0
+ CIHI + CO + CH,
+ CHS CO + 2H
+ CH CO + H
0
0
(28)
proceed and in all probability account for CO formation in this system.288

A study has also been made of laser emission from vibrationally excited
C0289formed in the reactions (29) and (30), the oxygen atoms being pro0
0
+ cs co + s
+ CSe +-CO + Se
---t
(29)
(30)
duced directly by flash photolysis of SO2.The production of CO fluorescence

286
288
28Q
290
291
292
H. Dubost and L. Abouaf-Marguin, Chem. Phys. Letters, 1972, 17, 269.

L. Lambert, C. Pepin, and A. Cabana, J. Mol. Spectroscopy, 1972, 44, 578.
S. J. Arnold and G. H. Kimbell, Canad. J . Chern., 1973, 51, 451.
S. Rosenwaks and I. W. M. Smith, J.C.S. Faraday 11, 1973, 69, 1416.
D. L. Judge and L. C. Lee, J. Chem. Phys., 1973,58, 104.
G. Hancock, B. A. Ridley, and I. W. M. Smith, J.C.S. Faraday 11, 1972, 68, 2117.
C. Morley, B. A. Ridley, and I. W. M. Smith, J.C.S. Faraduy 11, 1972, 68, 2127.
267
through photodissociation of Coghas been investigated using a line emission

source;290the fluorescence spectra so produced are presented and identified.
Finally, a study has been made of the i.r. chemiluminescenceemitted from
vibrationally excited CO, formed in the flash photolysis of N02-CS291
and N0,-CSe~g2mixtures according to the reaction sequence:
0
0
+ cx2
+ CX
xo + cx
CO
+X
(X = S or Se)
The emission spectrum from electronically excited CS, produced by energytransfer reactions of metastable argon atoms with CS2, COS, and CSCI,,
has been measured;293ina careful analysis of the spectrum soobtained, several
new bands were noted.
The mechanisms of the U.V. photolysis of C0294and the photoionization of
inter aliu CO by soft X-rays295have been investigated. The former reaction
has been examined by isotopic enrichment techniques and from energy-transfer consideration^.^^^ The latter has been studied using mass-spectrometric
techniques;295the ions produced by the absorption of 0.28, 1.25, and 1.5
keV X-rays were found to be CO+, C02+,C+,O+,C2+,and 02+.
1.r. spectroscopy and several other techniques have been used to study the chemical
nature of the solids produced by the radiolysis of CO both alone and admixed
with Fe(C0),.296 Very small concentrations of Fe(CO), have been shown to
change radically the products of the reaction; thus, whereas in the absence of
Fe(CO), the products are water-soluble, in its presence the products are inert.
The most prominent features of the i.r. studies of the Fe-free products are
absorptions indicative of C=C=C,
6 0 ,COO-, and possibly C=C;
these groups can be accounted for by the formation of a polymer built up
from carbon suboxide units. The major difference between the spectra of the
Fe-free products and the Fe-containing deposit is the absence of a C=O
absorption in the spectra of the latter. It is thus suggested that the iron bonds
with the oxygen of the C=O group; more than one oxygen could bond to the
iron, thus neighbouring molecules could be linked to give a solid of high
molecular weight and greater insolubility.296
Several investigations of the reaction of carbon monoxide with atoms,
radicals, and small charged species have been
the systems
which have been studied are summarized in Table 17.
2s3
294
295
2s6
2s7
2s8
2D9
300
301
302
303
304
305
G. W. Taylor, D. W. Setzer, and J. A. Coxon, J. Mol. Spectroscopy 1972, 44, 108.

0. Dunn, P. Harteck, and S. Dondes, J. Phys. Chem., 1973, 77, 878.
R. J. Van Brunt, F. W. Powell, R. G. Hirsch, and W. D. Whitehead, J. Chem. Phys.,
1972, 57, 3120.
T. Baird, Carbon, 1972, 10, 723.
J. J. Ahumada, J. U. Michael, and D. R. Osborne, J. Chem. Phys., 1972, 57, 3736.
W. B. Demore, J. Phys. Chem., 1972, 76, 3527.
A. A. Westenberg and N. DeHaas, J . Chern. Phys., 1973, 58,4061.
D. H. Volman and R. A. Gorse, J . Phys. Chem., 1972, 76, 3301.
A. A. Westenberg and N. DeHaas, J. Phys. Chem., 1972,76, 1586.
F. Stuhl and H. Niki, J. Chem. Phys., 1972, 57, 3671.
R. Simonaitis and J. Heicklen, J. Phys. Chem., 1973, 77, 1096.
E. Mukad, J. Chcm. Ph.ys., 1973, 58, 4374.
D. A. Parkes, J.C.S.Faraday I , 1973, 69, 198.
268

Table 17 Reactions of CO with atoms, radicals, and small charged species
Ref.
System
+ CO -+ HCO
+ co -+ co,
+ CO +COZ + H.
+ CO C02 + *OH
o++ co co++ 0 -
H*
0.
.OH
HO;
0,
+ coz + co
co, + co
cog + coa
CO;
+ co*
297
298
299-302
300,301, 303
304
305
305
The methanation of carbon monoxide by hydrogen has been studied by two

groups of w o r k e r ~ . 3 ~ - ~
Lett
~ * et d 3 0 6 examined the products of microwave
discharges in a flow system containing CO-H,-Ar mixtures by mass-spectroand
metric techniques. The formation of the major products, CH,, C2H2,
CO,, was studied as a function of reactant gas composition, pressure, microwave power, and flow rate. Maximum conversion occurred using a 3 :1 ratio
of H,:CO; increased microwave power enhanced C2H2formation at the
expense of that of CH, but most of the increased production above the
threshold power level consisted of H,O, CO,, and polymeric deposits. The
final product distribution is consistent with the presence of free-radical
have considered
reactions in the microwave discharge.306Bousquet et aZ?07*308
the effect of catalysts on this particular reaction; in particular, the catalytic
activity of nickel supported on active alumina has been assessed as a function
of nickel content. The mechanism of the catalysis is thought to follow the
sequence shown in Scheme 2. During the course of the reaction a surface
Reagents: i, Hs
Scheme 2
carbide, Ni,C, is formed by reaction of the catalyst with CH,; it has a low
reactivity towards hydrogen and thus effectively poisons the catalyst.50s
The oxidation of CO has been the subject of a wide variety of investigat
ranging from radiation-induced oxidation in CO-0, mixtures to
low-temperature catalytic oxidation on Sn0,-CuO gels. The electrochemical
R. G. Lett, W. A. Steiner, and Y. C. Fu,J. Phys. Chern., 1972, 76, 2941.
J. L. Bousquet and S. J. Teichner, Bull. SOC.chim. France, 1972, 3687.
J. L. Bousquet, P. C. Gravelle, and S. J. Teichner, Bull. SOC.clzim. France, 1972,3693.
309 E. I. Konnik, Rum. Chem. Rev., 1973, 42, 111.
310 C. Willis, A. W. Boyd, and P. E. Binder, Canad. J. Chern., 1972, 50, 3508.
311 E. A. Lissi, G . Hassiff, and A. E. Villa, J.C.S. Faraday I, 1973, 69, 346.
312 M. J. Fuller and M. E. Warwick, J.C.S. Chem. Comm., 1973, 210.
313 A. W. Sklyarov, J. Volter, and I. I. Tretjakov, Z . anorg. Chem., 1973, 396, 129.
314 J. S. Choi and B. W. Kim, Bull. Chem. SOC.
Japan, 1973, 46, 21.
306
307
308
Elements of Group ZV
269
oxidation of CO has been the subject of a comprehensive review;309the advances achieved recently in this technique are considered and the problems of
further improvement analysed. Electrochemical methods for analysis of CO
which are important for industry, medicine, and scientific research are also
reviewedFogThe results of an examination of the radiation-induced oxidation
of CO in high-dose-rateradiolyses of CO-O2 mixtures310are consistent with a
positive ion chain reaction, summarized in equations (3 1)-(40), similar to
that proposed for low-dose-rate studies involving OZ, CO;, and CO; as
chain carriers.
Ini tiation
JVV+ Of + e* CO+ + e0: + Oa + M + O f + M

0: + co -+ co,' +
COf + 0,
co:
co,' 3- co co: + c02
0 2
CO
Propagation
0 2
-+
--j
co; +
0; + c02
+ O2 + M 4 0 ; + M
O t + e-(or 0,)-+ 2 0 ( + 0 2 )
CO,' + e-(or 0;)--+ CO + 20(+02)
0 2 -+
e-
Termination
(33)
(34)
(3 5 )
(36 )
(37)
(38)
(39)
(40)
The kinetics of the oxidation of CO by methoxyl radicals (produced by the

thermal decomposition of dimethyl peroxide), as shown in equation (41),
+ CO
*CHBO
COa
+ *CHs
(41)
have been determined;311the data for the overall reaction can be rationalized
by a free-radical mechanism.
Three groups of authors have reported the results of catalytic investigations
of the oxidation of C0.31a414
Coprecipitated Sn0,-CuO gels, particularly
those with a Cu: Sn atomic ratio of between 0.5 :1 and 0.6:1, have been found
to be very active catalysts for the low-temperature (<lo0 "C) oxidation of
C0.312The importance of the adsorbed layer in the mechanism of the catalytic
oxidation of CO on Pt has been determined over a wide temperature range.313
Up to 150 "C,the Pt surface is completely covered by CO and the reaction
is poisoned; between 250 and 5OO0C the surface is saturated with active
oxygen and the rate of oxidation is independent of temperature. At higher
temperatures oxygen desorbs and the rate decreases. Adsorbed oxygen and
gaseous CO react according to an Eley-Rideal mechanism. A detailed study
of the kinetics and mechanisms of the oxidation reaction of CO has been
effected between 260 and 350 "C by means of the static method using n-type
ZnO semiconductor as a catalyst under various oxygen and CO pressures.314
The reaction mechanism can be explained in terms of the n-type character of
ZnO; firstly oxygen accepts electrons from the activated ZnO surface to be
adsorbed on the active sites [equation (42)]. Carbon monoxide then reacts
270
with the adsorbed 0-species, forming adsorbed CO, [equation (43)], which
is subsequently desorbed [equation (44)].
40z(g)
e- 3 O-(ads)
O-(ads)
CO(g) + CO,(ads)
CO,(ads) -+ CO2C@
+ e-
(42)
(43)
(44)
The interaction of CO with NO on the surface of Pt supported on A1203

has been investigated using i.r. spectroscopic te~hniques.3~~
The discovery of
the intermediates (a Pt-NCO species and an NCO- anion) provides a new
mechanistic pathway, equations (45)-(43),
which overall is summarized by
equation (49).
Pt/A12
NO(& +N(ads)
Wads)
-NCO(ads)
+ CO(g)
03
+ CO(g)
+ NO(g) ---+
2N0
+ 2C0
____+
Nads)
+ O(ads)
(45)
-NCO(ads)
(46)
CO2<@
(47)
N2(@
N2
+ COdg)
+ 2C02
(48)
(49)
The chemisorption of CO on met a1 surfaces, including molybdenum,316

t ~ n g s t e n , 3iron
~ ~ ,318
. ~ ~cobalt
~ ,316 nickel,3l9 and a series of iridium-palladium
a l l o y ~ , 3 ~has
~ - been
~ ~ ~studied using a variety of techniques, including X-ray
and Auger spectrosphotoelectron spectroscopy,316i.r.
copy.319The interaction of CO with S,323
and 0224on metal surfaces
has been investigated using i.r. spectroscopic techniques. Whereas the interaction between adsorbed CO and adsorbed S on a platinum surface is very
weak and does not lead to a surface
interaction of CO and NO on
platinum is very strong, leading to the formation of the surface species
Pt-NCO and the NCO- ani0n.3~~
The analysis324of the spectral results of
oxygen addition to chemisorbed CO on tungsten indicates that the CO is
displaced by the oxygen; thus tungsten does not behave like nickel where
oxygen addition to surface CO produces surface CO,.
Similar studies of the i.r. spectra of CO chemisorbed on metal oxides have
been carried o ~ t . A3group
~ ~of ~Russian
~ ~ workers
~
studied the chemisorption
316
M. L. Vinland, J. Phys. Chem., 1973,77, 1952.
316
S. J. Atkinson, C. R. Brundle, and M. W. Roberts, J . Electronic Spectroscopy, 1973,
317
318
31B
320
321
322
a23
324
326
326
2, 105.
C. G. Goymour and D. A. King, J.C.S. Faraday I, 1973, 69,736.
G. Blyholder and M. Tanaka, J. Phys. Chem., 1972, 76, 3180.
H. H. Maddon, J. Kiippers, and G. Ertl, J. Chem. Phys., 1973,58, 3401.
N. P. Sokolova, Russ. J. Phys. Chem., 1972, 46, 95.
N. P. Sokolova, Russ. J. Phys. Chem., 1972, 46, 557.
N. P. Sokolova, Rum. J. Phys. Chem., 1972, 46, 918.
H. P. Bonze1 and R. Ku, J. Chem. Phys., 1973, 58, 4617.
G. Blyholder and M. Tanaka, Bull. Chem. SOC.Japan, 1973,46, 1876.
D. V. Pozonyakov and V. N. Filimonov, Russ. J. Phys. Chem., 1972, 46, 587.
R. St. C. Smart, T. L. Slager, L. H. Little, and R. G. Greenler, J. Phys. Chem., 1973,
77, 1019.
271
of CO on both hydroxylated and dehydroxylated surfaces of MgO, A1203,
ZrO,, and Hf02?25The presence of structural OH groups was found to play
an important part in the chemisorption of CQ at temperatures above 250 O C ,
leading to the formation of surface formates; at lower temperatures, surface
carbonates predominate. On the other hand, on metal oxide surfaces free
from OH groups, CO is chemisorbed mainly in the form of bidentate carbonate, but bridged carbonates are also present. Smart et aZ.326have also
investigated the adsorption of CO on MgO. In this case the formation of
surface COi- groups was observed on samples prepared in high vacuum,
while added oxygen was necessary for C0:- formation with MgO which had
been subjected to more vigorous outgassing in ultrahigh vacuum. A comparison with the spectra of other magnesium compounds shows that the
surface COf- species formed are not the simple carbonate of the normal
MgCO, structure but have bidentate structures similar to Mg(C20,),2H20.326
?-Irradiation at 77 K in the presence of 20 Torr of 13C0 over well outgassed HY zeolite leads to a cation species identified with the CO+ radical.327
This radical has been characterized by extensive e.s.r. analyses; the data
would suggest that ca. 92.5% of the spin density is located on a 13C atom
o-orbit al.
Theoretical investigations of the electronic structures of C02,328COS,329
and CS,330*331
have been undertaken. The results of the analysis of the electronic structure of CS2 have been compared to the X-ray K emission and
absorption spectra of the CS2molecule;331the two sets of data are in reasonable agreement. X-Ray332and U.V. photoelectron spectraa3 of CO,, COS, and
CS, have been measured. The core-level electron spectra of these triatomic
molecules excited by Mg K, radiation have been
in an attempt to
identify and assign the shake-up satellite lines associated with ionization from
these levels. The valence spectra were also recorded and they too were found
to be rich in shake-up structure.332The U.P.S. of these molecules have been
measured as a function of the angle (0) between the direction of incident
photon and emergent p h o t ~ e l e c t r o n from
; ~ ~ the dependence of the band
intensity ( I ) as a function of 0 , the angular distribution parameter ((s) was
determined for each ionization band observed in the U.P.S:
I(0) cc 1
+ -2B ;(
sin2 0
- 1)
The value of the angular distribution parameter (B) ought to be a good

indication of the nature of the MO corresponding to a given electronic band
J. C. Vedrine and C. Naccache, Chem. Phys. Letters, 1973, 18, 190.
M. VuEeliC, Y. bhrn, and J. R. Sabin, J . Chem. Phys., 1973, 59, 3003.
329 P. G. Perkins, Rev. Roumaine Chim., 1973, 18, 1289.
330 P. G. Perkins, Rev. Roumaine Chim., 1973, 18, 1501.
331 L. N. Mazalov, A. P. Sadovski, V. M. Bertenev, K. E. Mironov, T. I. Guzhabina,
and L. I. Chernyavskii, J. Struct. Chem., 1972, 13, 802.
392 C. J. Allan, U. Gelius, D. A. Allison, G. Johansson, H. Siegbahn, and K. Siegbahn,
J. Electronic Spectroscopy, 1972, 1, 131.
ass T. A. Carlson and G. E. McGuire, J . Electronic Spectroscopy, 1973, 1, 209.
327
328
272
Inorgarric Chemistry of the Main-group Elements
in a U.P.S.;in the present study it was found that the MO containing sulphur
generally gave rise to substantially larger values of /3 than corresponding
orbitals containing
High-resolutiongas-phasevibration-rot ati~n-~~and electronicspectra337
of CS2 have been reported. The microwave spectra of 16013C32S,
1s012C32S,
and other isotopic species have been analysed and the following molecular
parameters derive0:33*r(C-O) = 1.15431 f 0.00024, r(C-S) = 1.56283 f
0.00037, r(0-S) = 2.71714 f 0.00013 A. A detailed i.r. spectral analysis
of the shapes and intensities of the fundamental bands v2 (CSC deformation)
and v3 (C-S antisymm. stretch) has been undertaken for liquid CS, and its
chloroform solution^.^^ The Raman spectra of polycrystalline samples of
CS2 at 18 and 7 9 K have been reported;=O the observed frequencies are
compared with those derived from lattice-dynamics calculations based on
atom-a tom interactions.
The dissociation of carbon dioxide induced by both a silent electric dischargew1 and photons of wavelength 812-1216
has been investigated.
The photoionization of inter a h CO, by soft X-rays has also been studied;=
the total and relative abundances of the thermal-energy ions produced by
absorption of 0.28, 1.25, and 1.5 keV X-rays in CO, (CO;, COi+, CO+, C-t,
O+, C2+)have been measured using a mass-spectroscopic technique. Measurements of relative S, concentrations following the flash photolysis of OCS
diluted with C0244have been used to investigate the mechanism of the polymerization of atomic sulphur, one of the principal products of the photolysis:
cos % co
+s
The fluorescence of carbon disulphide vapour has also been investigated,345

both in the presence and absence of foreign gases (e.g. Ar, N,, 02,CO,,
COS, SF,, and C,H,).
The formation of carbon dioxide aggregates via homogenous nucleation in
s34
338
337
338
339
s40
s41
s43
s4s
344
A. G. Maki. J. Mot. Spectroscopy, 1973,47, 217.

J. Giguere, V. K. Wang, J. Overend, and A. Cabana, Spectrochim. Acta, 1973,29A,
1197.
J. A. Creighton and T. J. Sinclair, Spectrochim. Acta, 1973,29A, 817.
G.Jungen, D. A. Malm, and A. J. Meirer, Chem. Plays. Letters, 1972, 16, 302.
A. G. Maki and D. R. Johnson, J . Mol. Spectroscopy, 1973,47,226.
M. Kakimoto and T. Fujiyama, Bull. Chem. Soc. Japan, 1972,45, 2970.
A. Anderson, P. J. Grout, J. W. Leech, and T. S. Sun, Chem. Phys. Letters, 1973,
21, 9.
N. K. Nikolaeva, M. P. Popovich, and Yu. V. Filippov, Russ. J. Phys. Chem., 1972,
46, 1234.
G.M. Lawrence, J. Chem. Phys., 1972,57, 5616.
R.J. Van Brunt, F. W. Powell, R. G. Hirsch, and W. D. Whitehead, J. Chem. Phys.,
1972,57,3120.
R. B. Langford and G. A. Oldershaw, J.C.S. Faraday I, 1973,69, 1389.
C.Lambert and G. H. Kimbell, Cunad. J. Chem., 1973,51,2601.
273
nozzle beams has been the subject of three reports.346348Dorfeld and Hudson
have carried out a theoretical and experimental investigation of the kinetics
of C 0 2 dimer formationN6 and small-cluster growth;% the observed dimer
concentrations are in good agreement with theoretical analyses;346observed
cluster populations could be accounted for by the theory, by adopting
sticking probabilities of ca. 3 x
for monomer impinging on dimer,
trimer, and tetrarner.= Stein and A r m s t r ~ n have
g ~ ~ considered
~
the structures
of the largest clusters which are produced; they are solid and have the structure of the bulk material (simple cubic). Based on diffraction data, the structure of clusters down to average sizes in the range of 300-450 molecules per
cluster can be treated as bulk phase. The average cluster diameter is 52 f 5 A,
which corresponds to 1600 molecules per cluster.348
Several investigations of the reactions of atomic oxygen with COS,349
CS2,349-351
and CSez52have been effected. The reactions of O(lD),produced
by U.V. photolysis of ozone, have been studied in dilute mixtures of 0,and
CS2 or COS in Xe or Ar matrices at temperatures between 15 and 60 K. 1.r.
spectrophotometry was used to identify the products.349 (Table 18). No
Table 18 Reaction products obtainedfrom 03-COS and 0,-CS, mixtures
Reaction mixture
0,-CS,
0,-COS
Reaction products
COSYSOz,SO3, (CO in minor amounts)
COz, CO,SO3, SO,
evidence was found for the species CS20 or CS02 analogous to the product
C03 obtained by addition of O(l0) to C 0 2 under similar conditions. It is
suggested that the primary reaction products are formed according to the
sequence of reactions (50)-(53).
Reaction (51) has also been studied using
O+
crossed molecular beamss0 The complementary reaction (54) has been

investigated351as part of the sequence (54), (55) by analysing the i.r. chemi-
+ cs
+s
O+CS~-+SO
0
cs 4 co
346
347
348
34B
350
351
362
(54)
(55)
W. G. Dorfeld and J. B. Hudson, J. Chem. Phys., 1973,59, 1253.

W. G. Dorfeld and J. B. Hudson, J. Chem. Phys., 1973,59,1261.
G . D. Stein and J. A. Armstrong, J . Chem. Phys., 1973, 58, 1999.
P. R. Jones and H. Taube, J. Phys. Chem., 1973,77, 1007.
P. L. Moore, P. N. Clough, and J. Geddes, Chem. Phys. Letters, 1972, 17, 608.
G. Hancock, B. A. Ridley, and I. W. M. Smith, J.C.S. Faraday II, 1972, 65, 2117.
C. Morley, B. A. Ridley, and I. W. M. Smith, J.C.S. Furaday 11, 1972, 68, 2127.
274

luminescence emitted from the vibrationally excited CO product. The analogous 0-CSe, system has also been examined in an identical
Negative-ion reactions in 02-c02,35302-C0-C02,353 and N20-co2354
mixtures have been examined by Parkes. The kinetics of the reactions
(56)-(62) have been studied for near-thermal ions in a drift tube and mass
+ 2 c 0 2 4 COT + co,
0; + co, + co -+ co, + cop
NO- + 2C0,
COz,NO- + CO2
NO- + CO,
NO + CO, + eNO- + COZ + NzO
CO, + N, + NO
NO- + COZ + NzO
N302 + COZ
NO- + COZ + NZO + COZ, NO- + NZO
0,
(56)
(57)
(58)
(59)
(60)
(61)
(62)
filter. The electron affinity of inter aZia CS, (0.44& 0.2 eV) has been derived
from endothermic negat ive-ion charge-t ransfer reactions.355
A facile C 0 2 insertion into the Cu-0 bond of cupric dimethoxide
Cu(OMe), in a specific solvent (pyridine) to form a cupric methyl carbonate
in which the COz moiety is labile has been reported:356
Cu(OMe),
+ 2C0,
Room temp.,
Cu(OC0 OMe),
p yridine
The formation of the product was confirmed by chemical and spectroscopic

examination.
The electrolytic reduction of CO, in neutral aqueous solution at a mercury
pool cathode has been studied to establish the reaction mechanism and to
obtain kinetic parameters by a steady-state galvanostatic method.357The most
plausible reaction is thought to involve the consecutive charge-transfer
steps:
C02
H20
e- + H,CO,(ads.) + OHHCO,(ads.)
e- + HCO;
+
+
A number of spectroscopic studies of surface species formed when GOz is

and metal
adsorbed by both metals358D359
have been reported.
D. A. Parkes, J.C.S. Faraday I, 1973, 69, 198.
D. A. Parkes, J.C.S. Faruday II, 1972, 68, 2121.
355 B. M. Hughes, C. Lifshitz, and T. 0. Tiernan, J . Chem. Phys., 1973, 59, 3162.
356 T. Tsuda and T. Saegusa, Znorg. Chem., 1972, 11, 2561.
367 J. Ryu, T. N. Anderson, and H. Eyring, J. Phys. Chem., 1972, 76, 3278.
368 I. A. Ostrovskaya, V. 1. Lygin, and N. P. Sokolova, Russ. J. Phys. Chem., 1973, 47,
232.
36Q V. F. Khorkov, G. D. Lyubarskii, Yu. A. Mishchenko, and A. I. Gelbshtein, Russ.
J . Phys. Chem., 1972,46,269.
aao Y. Huang, J . Phys. Chem., 1973, 77, 103.
s61 T. T. Chuang, I. G. Dalla-Lana, and C. J. Liu, J.C.S. Faraday I, 1973, 69, 643.
362 Ya. M. Grigorev, D. V. Pozonyakov, and U. N. Filimoncv, Russ. J . Phys. Chern.,
1972, 46, 186.
363 Y . Fukuda and K. Tanabe, Bull. Chem. SOC.Japan, 1973, 46, 1616.
3 6 4 K. Sogabe, A. Iiasegawa, Y. Yamada, and M. Miura, Bull. Chem. SOC.Japan, 1972,
45, 3362.
3b3
354
275
The adsorption of CO, on metallic nickel films has been studied in both the
presence358and absences59of oxygen. An i.r. spectroscopic
of the
simultaneous adsorption of CO, and 0,on nickel has shown the formation of
carbonate-carboxylate structures on the nickel surface. The adsorption of
CO, on nickel in the temperature range -196 to 0 0C359has been found to be
irreversible, the molecules being adsorbed at two surface sites within the
limits of the monolayer. Above 100 O C , dissociative adsorption of CO, takes
place with the formation of C0.359
The interactionsbetween C 02and the specificadsorption sites onamorphous
silica-alumina (containing 13.2 %Al,03) were studied by measurement of
adsorption isotherms over a temperature range from 0 to 290C.360These
adsorption sites were found to be < 1 % of the surface and yielded an enthalpy
of adsorption of 14.5 kcal mol-l. The major contribution of the adsorbateadsorbent interaction was attributed to quadrupole energy; entropy calculations showed that the adsorbed CO, was localized with almost no rotational
degree of freedom. The poisoning of 7-alumina by CO, has been shown to
suppress the catalytic reaction:3g1
2cos + so,
--f
(3/X)S,
+ 2c02
Using i.r. spectroscopicevidence, a reaction mechanism has been proposed in

which SO, is adsorbed on hydroxyl sites and COS adsorbed on aluminium
ion sites; it is the blocking of the latter sites by chemisorption of CO, which
poisons the catalyst.
Two groups of authors have reported the results of i.r. studies of the surface
compounds formed when CO, is chemisorbed on metal oxides;3G2-3G3 Russian
workersag2have studied the adsorption on both hydroxylated and dehydroxylated BeO, MgO, A1203,Ga203,In,03, TiO,, ZrO,, and HfO,. Unidentate,
bidentate, and bridging carbonates are observed on both hydroxylated and
dehydroxylated surfaces. In the presence of hydroxy-groups, however, a
surface hydrogen carbonate is formed on all the metal oxides with the exception of Ti02.362The i.r. spectra of CO, absorbed on MgO and CaO have been
measured in the region 700-4000cm--1 at varying amounts of CO,, and
temperatures of absorption and desorption by a group of Japanese workers.3G3
They observed that both unidentate (10) and bidentate (11) carbonates are
formed on MgO when small amounts of C 0 2 are adsorbed, the unidentate

species predominating as the concentration of CO, is increased. On the other
hand, only unidentate species were formed on CaO at room temperature
independently of the amount of adsorbed CO, ; bidentate species were also
lo
216
formed on CaO, however, when the adsorption temperature was high. The
unidentate carbonates formed on both oxides at room temperature partially
changed to bidentate carbonates on evacuation at higher temperatures.363
The formation of the CO; anion radical364on various cation-exchanged
X-type zeolites has been interpreted on the basis of a mechanism involving
the initial trapping of the electrons by the zeolite surface on 7-irradiation,
followed by electron transfer to COz molecules. The structure of the CO;
species has been investigated by e.s.r. spectroscopy; the results show that the
interaction of the COT radical with the zeolite changes with the electrostatic
field (i.e. cation exchange) on the surface.364
Carbonates, Thiocarbonates, and Related Anions. The syntheses of carbonates,
hydroxide carbonates, and oxide carbonates have been reported. Those
factors which influence the crystallization of rare-earth carbonates have been
investigated;365the carbonates were precipitated at various temperatures from
aqueous solutions by using sodium carbonate (2Q-80 "C), sodium bicarbonate (20-80 "C), trichloroacetic acid (40-120 "C), and urea (50-150 "C)
as precipitants. The carbonates so formed were characterized by chemical
analysis and X-ray powder diffraction techniques. It was found that they
could be classified into several phases (Table 19) according to the ionic radii
Table 19 Crystalline rare-earth carbonates

Rare-earth present
TYPe
Lanthanite, Ln,( C03)3,8H,0
Tengerite, Ln,(CO,),,nH,O ( 2 n < 3 )
Monoxocarbonate, Ln,0(C03),,nH,0 (1 Q n Q 2 )
Hydrated double carbonate of Na and Ln
<
La, Ce
Nd, Sm, Gd, Dy, Ho, Er
La, Ce, Nd, Sm
La, Ce, Nd, Sm, Gd, Dy, Y
of the rare-earth elements and the preparation temperatures. It was also

observed that the concentrations of the rare-earth ion in the solutions and the
ageing periods affect the cry~tallization.~~
The hydroxide carbonates SC(OH)(CO,),~H,O~~~
and 3PbCO,,Pb(OH),,Na,C0267 have been prepared together with the oxide carbonate PuO,(CO,),0-0.5H20.368 All three products have been characterized by both physical
and chemical techniques. The unit-cell parameters of PuO,(CO,),0-0.5Hz0,368which is orthorhombic, are listed in Table 20, together with
those of (NH,),UOz(C03),,369KzC03,370and T13F(C0,),3'l all of which have
been found to be monoclinic.
366
366
367
368
36s
370
371
K. Nagashima, H. Wakita, and A. Muchizuki, Bull. Chem. SOC.Japan, 1973,46, 152

L. N. Komissarova, E. G . Teterin, V. M. Shatskii, and V. A. Zhorov, Russ. J . Inorg.
Chem., 1972, 17, 191.
V. I. Bukakhova, E. Ya. Ben'yash, M. M. Shokarev, and I. I. Vershinina, Russ. J.
Inorg. Chem., 1972, 17, 1 1 .
J. D. Navratil and H. L. Bramlet, J. Inorg. Nuclear CIim., 1973, 35, 157.
R. Graziani, G. Bombieri, and E. Forsellini, J.C.S. Dalron, 1972, 2059.
B. M. Gatehouse and D. J. Lloyd, J.C.S. Dalton, 1973, 70.
N. W. Alcock, Acta Cryst., 1973, B29,498.
277
The kinetics and mechanism of the transformation of aragonite, CaCO,,

(containing 0.025 % Na) into calcite have been investigated using d.t.a., X-ray
diffraction, and i.r. spectroph~tometry.~~~
The transformation temperature
(476 "C) and the energetics of the transformation (AH = 85 kcal mol-l and
Ea = 98 kcal mol-l), as determined from the differential thermal curves, are
in approximate agreement with previously reported values. A complementary
Table 20 Unit-cell parameters of PuO~(C0,),0-0.5H20, (NH,),UO,(CO,),,
K2C03, and T1,F(CO3)
Compound
alA
4.80 =t: 0.01

PuO,(CO~),O--O.~H~O
(N H & U~ Z ( CO S) ~
10.64
5.64
KzC03
7.510
Tl3F(CO3)
blA
CIA
9.26 f 0.02
9.38
9.80
7.407
4.25 f 0.01
12.85
6.88
6.069
Ref.
368
96'27' 369
98.8' 370
120.0' 371
thermodynamic and kinetic analysis has been made of the reasons for the
formation of aragonite in the metastable region373(i.e. when it forms together
with calcite in an alkaline aqueous solution at temperatures up to 100 "C).
It is concluded that the main cause of the appearance of aragonite is related
to the relative kinetics of the crystallization of the two crystal forms.
The preparation of pure Me4N+CS,, its stability range, X-ray diffraction,
and i.r. spectra have been r e ~ o r d e d . 3The
~ ~ preparation and characterization
of strontium perthiocarbonate (SrCS4,nH20)in a pure form have also been
d e s ~ r i b e d ; ~three
~ s hydrates SrCS,,nH20 (n = 2, 3, or 4) as well as the anhydrous material have been prepared. The anhydrous product was obtained
by treating directly a suspension of Sr(OH),,8H20, previously saturated
with H2S, with an excess of CS2 and S ; the crude product was purified and
dried under vacuum in the presence of P20,. Hydration of this product gave
rise to the three hydrates.
Two theoretical analyses of the electronic structures of carbonates and
related species have been p ~ b l i s h e d Russian
. ~ ~ ~ ~workers376
~ ~ ~ have reported
the results of MO calculations of the isoelectronic series of oxy-anions
BOZ-, Cog-, and NOT. The derived data, when compared to the results of
X-ray spectral investigations, accurately describe the principal characteristics
of the spectra. perk in^^^^ has studied the electronic structure of inter alia
H2CS,, CSg-, and CSi- using a self-consistent MO method. Perhaps the most
interesting conclusion to come from the investigations is the fact that the
molecule H2CS3is shown to be quite stable.
372
373
574
376
976
311
M. S. Rao, Indian J. Chem., 1973, 11, 280.

D. F. Korolev, Russ. J . Phys. Chem., 1972, 46, 1208.
M. Robineau and D. Zins, Compt. rend., 1973, 276, C , 1293.
D. Zins and M. Robineau, Compt. rend., 1973, 276, C , 951.
S . P. Dolin and M. E. Dyatkina, J. Struct. Chem., 1972, 13, 906.
P. G. Perkins, Rev. Roumaine Chim.,1973, 18, 1501.

278
A number of vibrational spectroscopic studies of carbonates and related
anions have been undertaken and described during the period of this Report.378-3s3The laser Raman and i.r. spectra of the alkali-metal bicarbonates,
MHCO,, and carbonates, M2C03 (M = Li, Na, K, Rb, or Cs) in both H 2 0
and D,O have been determined at 25 OC for each salt over the concentration
range 0.01 moll-1 up to saturation.378The carbonate spectra show pronounced
changes with increasing concentration, which have been attributed to the
perturbation of the D,, symmetry of the carbonate ion. This perturbation is
interpreted in terms of solution and ion pairing of the carbonate ion. There
was no evidence for similar interactions in the HCO, solutions. A somewhat
similar i.r. investigation of inter alia C0:- in host lattices of alkali-metals and
alkaline-earth metals with other oxyanions (Table 21) has been carried
Table 21
singlet v3
doublet v3
21,
band of C0:- situated in host lattices

K2Cr04
K~MoO,,K~WO,
P-RbzWOI
Rb2Cr04,cc- Rb2MoOr, or-Rb,WO,
Cs,Cr04
Dilute solutions of COf- anion in the host lattices have been prepared, the
substitution of the guest anion on the lattice anion positions being monitored
by i.r. examination. The v, vibration of the C0:- anion appears as a sharp
singlet or doublet, depending on its splitting by the site group of the host
lattice; the splitting and the position of the bands allows a partial discussion of
the interaction between host lattice and C0i-.379 The frequency of the v2 i.r.active out-of-plane mode of the planar CO, species has also been studied in a
variety of co-ordination and site-symmetry
A tentative correlation
with possible diagnostic applications is drawn between the v2 frequency and
the site-symmetry/co-ordination type.
The i.r. spectra381of the crystalline thiocarbonates BaCS,, T12CS,, PbCS,
(two modifications), and CdCS,, and the Raman spectra382of CSi- (in
solution and of crystalline Tl,CS,) CS2Se2- (in solution and of crystalline
BaCS2Se), and crystalline BaCSe, have been measured and analysed. By
I3C substitution it was possible to assign all the observed i.r. bands and to
obtain information about the interaction of anion vibrations in the crystal.=l
The Raman spectra of BaCS2Se have allowed a reassignment of its previously
reported i.r. spectrum.m2The present assignment was supported by the calculation of the frequencies of CS,Se2- using Green's function method and
also by transferring the valence force-field constants from CSi- and CSei-.
The earlier reported frequencies and assignments for CSSez- have been analysed in the same way; it could be demonstrated that the vibrational spectrum of BaCSSe2cannot be completely correct.382
378
a79
380
381
388
383
B. G. Oliver and A. R. Davis, Cunud. J . Chem., 1973, 51, 698.

H. J. Becher, F. Friedrich, and H. Willner, 2. unorg. Chern., 1973, 395, 134.
P. C. Healy and A. H. White, Spectrochim. Acta, 1973, 29A, 1191.
J. Horn and W. Sterzel, 2. anorg. Chem., 1973, 399, 211.
A. Miiller, N. Mohan, P. Cristophliemk, I. Tossiois, and M. Grager, Spectrochim.
Actu, 1973,29A, 1345.
B. P. Choudhari, M. C. Vaidya, and D. S. Datar, Indian J . Chern., 1972, 10, 731.
279
In view of the conflicting reports about the nature of basic magnesium
carbonates, a group of Indian workers undertook both i.r. and X-ray diffraction studies of these
It is concluded that the light product is
wholly composed of hydromagnesite whereas theheavyproduct is an equilibrium mixture of hydromagnesite and magnesite, MgCO,. Thermal and i.r.
studies suggest the chemical formula 3Mg(OH)(HCO,),Mg(OH), for hydromagne~ite.~,
The effect of additives (the eleven halides LiCl, NaCl, KCl,
RbCl, BeC12,4H20, MgC12,6H20, SrC12,6H20, BaC1,,2H2O, MgF,,
MgBr2,6H,O, and MgI,) on the thermal decomposition of basic magnesium
carbonate:@ designated as 4MgC0,,Mg(OH),,4H20, has been studied by a
group of Japanese authors by means of thermogravimetry, d.t.a., and gas
chromatography.384
The thermal decomposition of several carbonates, including RbHC0,,aS6
C S H C O , , ~ La,(COd,,0.25H,0,a86
~
Zr20,(OH)6-22C03,nH20,w7
and the
coprecipitated Ag2C0,-CdC0, mixture,388as well as that of basic magnesium
carbonate already described, has been investigated. That of the alkali-metal
bicarbonates [reaction (63)] has been studied by chemical analysis, X-ray
diffraction, and d e r i ~ a t o g r a p h yThe
. ~ ~ calculated apparent activation ener2MHCOa
MpCO,
+ COa + HZO
(63)
gies forthe thermal dissociation of MHCO, (M = Na, K, Rb, or Cs) increase

in going from NaHCO, to CsHCO, (Table 22).
Table 22 Apparent activation energies for MHC03(M = Na, K, Rb, or Cs)
MHCOt
EJkcal mol-l
NaHCO,
KHCOs
RbHCO,
CsHCO,
21.4
21.6
22.8
24.3
The thermal decomposition of lanthanum carbonate:386

Laa(CO&,0.25HzO
La,O,(CO,)
La20a(C03) 2COp
La,O,
CO,
+ 0.25HzO
has been studied in atmospheres of water vapour, CO,, and argon. Water
vapour was found to accelerate conversion of the carbonate into the dioxide
monocarbonate but to slow down the conversion of the latter into La203
At high pressures, COz retards both stages of the reaction but at low pressures, like argon, it accelerates the first stage. These effects are thought to be
related to diffusional hindrances to the reaction, to crystallization of the new
384
385
K. Amita and G. Hashizume, BUN. Chem. SOC.Japan, 1973,46, 1964.

V. A. Pushnyakova, A. S. Berger, and A. N. Kirgintsev, Russ. J. Inorg. Chem., 1973,
18, 164.
386
V. V. Samuskovich, E. A. Prodan, and M. M. Paulyuchenko, Russ. J . Inorg. Chem.,
387
V. N. Pokhudenko, L. I. Fedoryako, I. N. Tselik, and I. A. Sheka, Russ. J. Inorg.

Chem., 1972, 17, 1359.
G . Pannetier and D. Fgtu, Rev. Roumaine Chim., 1972, 17, 1805.
1972, 17, 1075.
38B
280
phase, and to the removal of residual water.38sOn heating the basic zirconium
carbonate Zr20,(OH),2,(C03),nH203s7the compound decomposes, the
main bulk of the water and C 0 2 being removed in the range 60-170 "C
and the remaining OH- groups being eliminated in the range 3 0 0 4 0 0 'C.
Decomposition terminates at 400-500 "Cwith the formation of ZrO,.
The reactions of several carbonates with simple gases have been conIt has been observed that the reaction of NOCl with AgzC03,
T12C03, and PbCO,Ssg proceeds via the intermediate formation of Nz04,
which has been detected spectroscopically, according to the two routes
shown in reactions (64)and (65) [summarized as (66)] and reactions (67) and
(68) [summarized as (69)], reaction (66) predominating over (69). The overall
+ 2NOCl
+ 2NO2 -+
+ 4NOC1 -+
+ 2NOC1
Ag,C03
AgzCOS
3AgzCOa
Ag2C03
Ag,COa
3AgtC03
+ +
+
+
+
+
+ +
+
+
+
+
+
2AgCl
C02
NO
NO2
2AgNOs
NO
COI
2AgN03
4AgC1
3N0
3c02
3 2AgCI
COP NO
NOs
2NOz 3 AgNOt
AgNOa
COS
4NOC1 4 4AgCl
AgNOs
AgNOa
3C0,
.--f
(64)
(65)
(66)
(67)
(68)
2 N 0 (69)
reactions of NOCl with thallium(1) and lead(I1) carbonates are designated as

follows :
8T12CO3
4PbCOs
+ 18NOC1
+ 6NOC1
--j
+ 4TlNOo + 14N0 + 8COz

+ Pb(NOs)2 + 4COa + 4 N 0
3Tl,[TICItJ
4 3PbC14
Nz04 never being observed. The reaction of sulphur dioxide with calcium
carbonate390has been shown to follow the primary reaction sequence
CaCO,
2[CaSO,]
+ SO, -+[CaSO,] + CO,

+ SO, 2CaS0, + 4S2
3
Traces of CaS, which appear in thin beds of CaCO,, are thought to be due to
a secondary reaction of S2 with CaO produced by the thermal decomposition
of CaCO,, viz.
CaCO, -+ CaO
2 ~ a 0 2s 3 2CaS
+ COP
+ So2
The comparative reactivities of the alkali-metal carbonates M&O, (M =

Li, Na, or K) towards A1203have been determined using thermogravimetric
techniques;391the carbonates can be arranged in the sequence of decreasing
reactivity Li,CO, > Na,CO, > K,CO,. The solid-solid reactions involving
BaCO, and iron(n1) oxide or A1203have also been studied in an attempt to
analyse the changes occurring at surfaces during this type of reaction.392
J.-P. Dumaullard and R. Perrot, Compt. rend., 1973, 276, C, 1417.
J. Tarradellas and L. Bonnetain, Bull. SOC.chim. France, 1973, 1903.
39L E. K. Belyaev, and V. F. Annopol'skii, Rum. J . Inorg. Chem., 1972, 17, 1078.
3s2 J. Beretka and M. J. Ridge, Austral. J. Chem., 1973, 26, 1353.
38Q
sQO
281
The reactions of aqueous solutions of M2C03 (M = Na or K) with
CaWO, z13
MaCOS CaWO, -+CaCO,
M,WO,
and of aqueous solutions of (NH4),C0, with rare-earth metal chlorides
LnCl, (Ln = Tb, Tm, or Lu)3g4have been investigated. It has been established
that in the LnC13-(NH,),C03-H20 system, thenormal carbonates Ln,(CO,),,4H20areformedatCO~-:Ln3+ratiosof1.5, whereas at ratios >2theproducts
are the double carbonates (NH4)Ln(C0,),,3H,0 and (NH,)Ln(C03)2,2H20.394
The behaviour of COT anion radicals generated in the flash photolysis of
carbonatoarnine complexesof CoI, [ e g . Co(NH,),CO,]+, [Co(NH,),CO,]f,
and [Co(en),CO,]f, in aqueous solution has been the subject of further
The species has been characterized by its absorption spectrum
(A,,,
= 600 nm) and its second-order decay kinetics. From an analysis of
the behaviour of C o g in aqueous solutions it is concluded that at pH 7 the
radical must exist in its acidic form CO,H, with pK, = 9.6 f 0.3.
The phase relationships in the systems Li,C03-(NH,),C03-H20,996
Li2C03-(NH,),C03-Li2S04-(NH,),S0,-H20,
396 and KHC0,-KSCN-H,0397
have been studied at 25 C.In the first system39ethe compound Li2C0,,3(NH4),CO, was found to crystallize, in addition to the simple salts; in the
second system396the boundaries of the crystallization fields of the compounds
Li2C03; Li2S04,H,0; Li,SO,,(NH,),SO,;
(NH4)2S04,(NH4)2C0,,H20;
and Li2C03,3(NH,),CO, have been established.
Derivatives of Group V Elements.*-Canagen

and Cyanides. Although the
data accumulated during the period of this Report describing this particular
topic can be neatly divided into spectroscopic and chemiczl properties, a
surprisingly high proportion of the reports contained in the latter section
concentrate on the react ions of the cyanogen halides. High-resolutionvapourphase rotation-vibration spectra of c y a n ~ g e nand
~ ~hydrogen
~
cyanide399*400
have been measured. The temperature dependence of the fundamental i.r.
absorption intensities of the v1 mode in monomeric and dimeric forms of
HCN vapour has been used to calculate a vapour-phase dissociation energy
of (HCN), as AED = -3.80 f 0.16 kcal mol-l. This value, although sornewhat greater than the previously reported experimental value of -2.6 kcal
mol-l, compares favourably with a recently theoretically computed value of
-3.7 kcal mol-l. Further analyses of the U.V. spectra of both ~yanogen*~l
* Data associated with CN or NCO etc. only.
3g3
394
395
396
3n7
308
399
0
*01
F. M. Perelman, M. E. Dorogov, and 2. G. Karov, Russ. J . Inorg. Chem., 1972, 17.

1452.
G. F. Deineka, I. N. Tselik, and E. P. Ilinskaya, Russ. J. Inorg. Chem., 1972,17,670,
S. Chen, V. Cope, and M. Z. Hoffman, J. Phys. Chem., 1973, 77, 1 1 1 1 .
A. Partala, T. A. Shuko, V. E. Plyushchev, and V. P. Artemev, Russ. J. Inorg. Chew.,
1972,17,1043.
P. S. Bogoyavlenskii and E. D. Gashpur, Rum. J. Inorg. Chem., 1972, 17, 1607.
L. H. Jones, J. Mol. Spectroscopy, 1973, 45, 55.
V. K. Wang and J. Overend, Spectrochim. Acta, 1973, 29A, 687.
H. D. Mettee, J . Phys. Chem., 1973, 77, 1762.
J. A. Meyer, D. H. Stedman, and D. W. Setzer, J. Mol. Spectroscopy, 1972, 44, 206.
282
and cyanide radica1s4O2have been reported. The cyanide radical has also
been investigated using microwave-optical double-res~nance,~~~
microwave
magnetic resonance,404and fluorescence excitation spectroscopy.405
The microwave spectra of ICN,406 NC-N0,4O7and NC.NC0408have been
recorded and analysed; the structures of NC-NOao7and NC.NC0400shave
been derived from the experimental data. The most striking structural feature
of NGNO is the distinct bend at the carbon atom407(12); a similar distortion
is found in F,N-CN. The nitrile link is a little longer than is common; it is
(12)
certainly longer than that found in NOCl (1.139A) and slightly longer than
that in H3C.N0 (1.213A). The central C-N distance is quite close to the
corresponding parameter in F2N-CN(ca. 1.39 A) and the angle CNQ to the
structural angle of NOCl (113" 20'). The structure of NC-NCO is of considerable interest since, although simple valence-bond theory suggests the
molecule is likely to be bent (13), it is isoelectronic with the linear C 3 0 2and
could therefore quite reasonably be linear, of structure either (14) or (15).408
The microwave data show the molecule to have a bent structure; there is,
however, evidence of a considerable tendency towards linearity. Thus it seems
likely that there are contributions from resonance forms (14) and (15) as
well as from (13), which presumably predominates.408
The bimolecular dissociation of (CN), behind incident shock waves40g
and the reaction of (CN), and H, behind reflected shock waves4l0have been
studied. An analysis of the dissociation data (obtained in the temperature
range 2200-3700 "C) results in the dissociation energy of the C-C bond,
Do(NC-CN) = 125.5 f 1.0 kcal mol-1.409The metathetical reaction:
(CN), + HI + 2HCN
*03
404
406
406
L. H. Schoonveld, J . Chem. Phys., 1973, 58, 403.

P. Meakin and D. 0. Harris, J. MoI. Spectroscopy, 1972, 44, 219.
T. J. Cook and D. H. Levy, J . Chem. Phys., 1973,58, 3547.
N. M. Jackson, J. Chem. Phys., 1973, 59,960.
J. B. Simpson, J. G. Smith, and D. H. Whiffen, J. Mol. Spectroscopy, 1972,44, 558.
R. Dickinson, G. W. Kirby, J. G . Sweeney, and J. K. Taylor, J.C.S. Chem. Comm.,
1973, 241.
408
409
410
N. H. Hocking and M. C. L. Gerry, J.C.S. Chem. Comm., 1973, 47.

T. Fueno, K. Tabayashi, and 0. Kajimoto, J . Phys. Chem., 1973, 77, 575.
J. M. Brupbacher and R. D. Kern, J. Phys. Chem., 1973,77, 1329.
283
has been studied by shocking equimolecular amounts of reactants in the
presence of an inert-gas diluent over the temperature range 1850-2650 0C.410
The reaction of cyanogen with active nitrogen411 has been studied using a
low-pressure flow reactor with on-line mass-spectrometric observation of the
reactants and products using various isotopically labelled (CN), species. The
reaction mechanism [reactions (70)-(78)] is thought to describe the principal
features of the reaction best. Gas-phase reactions of CN' radicals with cyElements of Group IV
N:
+ (CN), --+
2CN
+ (CN), -+
C8N:
N' + CN + N2
C'
CaN:
+ N2
+ C'
+ Na + C3N2 + NZ
+ CN'
C3N: -+ C2N'
C2N'
N' 4 2CN'
C3N2
N -+ (CN),
2C2N'
Nz 4 C,NZ
C, C3N2, C2N, CN +- Polymer
+
+
+ CN'
+ N2
(Cl.16N),,
anogen,"l2oxygen,412rnethane,4l3and ethane413have been investigated as a

function of temperature and vibrational excitation of the radical. The results
of the study are summarized in Table 23.
Table 23 Reactions of CN' radicals
Reaction
CN.
CN'
CN'
CN'
++ (CN),
0 2
+ CHI
+ CzHs
Activation eneugy/kJ mol-1
13.1
0
8.3
<0.8
Ref.
412
412
41 3
413
A fascinating e.s.r. investigation of the reactions in irradiated aqueous

solutions of HCN and the CN- anion has been effe~ted.4~~
Use of the in situ
radiolysis-e.s.r. method has shown that the primary radicals, H' and 'OH
(from the radiolysis of H20), add to HCN in acid solutions to yield the
H2C=N' and HC(OH)=N' radicals. The other intermediate, eZq, also leads
to H,C==N' by addition followed by protonation. Thereaction of 'OH andowith CN- in alkaline solutions was found to produce a radical which is most
probably 'CONH, (or 'CONH-). This radical is the same as that obtained
from the reaction of 'OH with formamide. It is not clear as to whether the
intermediate HC(OH)==N can rearrange to CONH,, but the reverse reaction
is not found. Thus in experiments with HCONH2, the radical CONHz is
found under conditions where HCN yields HC(OH)==N>l4 A theoretical
411
(12
(13
414
M. Berger and G. B. Kistiakowsky, J. Phys. Chem., 1973, 77, 1725.

G. E. Bullock and R. Cooper, J.C.S. Furuduy I, 1972, 68, 2175.
G. E. Bullock and R. Cooper, J.C.S. Furuduy I, 1972, 68, 2185.
D. Behar and R. W. Fessenden, J. fhys. Chem., 1972, 76, 3945.
284
investigation of the C==N double bond which is found in several of the

above radicals has been undertaken.415In particular, ab initio Gaussian-type
calculations have been completed for the ground and excited states of the
hypothetical molecule formaldimine, H2C=NH, which is thought to be the
simplest system with a G=N function.
An investigation416of the behaviour of HCN (a non-electrolyte) in anhydrous HF has shown it to be protonated in the presence of BF, and AsF,;
unstable solids believed to be HNCH+ BF; and HCNH+ AsF; have been
prepared. In solution in anhydrous HF, HCN slowly adds HF to form the
cation F2HCNHz, which has been isolated as the AsF; salt. Further slow
reaction occurs in solution to form a polymer containing CF,H.NH groups.
A review of the reactions of cyanogen halides in inorganic chemistry has
been published;417the results described deal with reactions involving metallic
and non-metallic elements, compounds, and ions. Hydrolysis and polymerization reactions as well as synthetic procedures are also discussed. The
results of five independent investigations of the chemistry of the cyanogen
halides have been reported in the literature. A novel, yet simple, synthesis of
CNF is described in a papeF8 which discusses as its major feature the
molecular rot at ional Zeeman effect in 12C15NF.Approximately equal pressures of HCN and ClF, (maximum pressure 5-6 Torr) are mixed in an
enclosed glass tube and a Tesla coil placed near the outside of the tube to
cause discharge in the mixture. The products are then passed into a waveguide
and pumped to ca. 5-10 ,u final pressure; the CNF thus prepared has a
half-lifetime of approximately 5 minutes.
The hydrolysis of CNCl has been studied in buffered media.*l9 Rate
equations have been derived, general base catalysis has been identified, and
the activation energy of the uncatalysed reaction at pH 10.1 has been determined as 59.1 f 0.5 kJ mol-l. The effects of several additives on the rate of
hydrolysis have been examined. The chlorine-catalysed hydrolysis has been
investigated and the catalytic species conclusively identified as dissolved
molecular chlorine. The reaction of sulphite anions with CNCl has been
shown to involve the formation of a stable add~ct.~*O
Although it has hitherto
proved impossible to isolate and characterize the adduct, it appears to contain
CNCl and SO:- anion in the ratio of 2:2. To account for the stability of the
compound at pH < 9, a cyclic structure (16) is likely, having a six-membered
S-N-Cl
ring. At higher pH values, the adduct decomposes to regenerate
sulphite anions. The formation and decomposition of the adduct have been
studied by kinetic analysis, from which Scheme 3 is proposed.
Activation energies have been derived for the formation and decomposition
reactions, viz. EA(formation) = 54 kJ mol-l, E,(decomposition) = 58.3
415
416
417
418
*19
4a0
R. Macauly, L. A. Burnelle, and C. Sandorfy, Theor. Chim.Acta, 1973, 29, 1.

R. J. Gillespie and R. Hulme, J.C.S. Dalton, 1973, 1261.
J. MacCordick, Bull. Soc. chim. France, 1973, 55.
S. L. Rock, J. C. McGurk, and W. H. Flygare, Chern. Phys. Letters, 1973, 19, 153.
P. L. Bailey and E. Bishop, J.C.S. Dalton, 1973, 912.
285
kJmol-l. This latter value is remarkably close to that obtained for the
hydrolysis of CNCl in the same medium (59.1 kJ m~l-l).~~O
Pyrolysis of CNBr in argon diluent has been studied both experimentally
and theoretically:421for mixtures with concentrations greater than 5 % CNBr,
pyrolysis occurs by a simple chain mechanism. For more dilute mixtures, a
Cl-CEZN
CNCl
+ SO:
s2-
CI-C=N
0- ()
/ O
CI-C=N-S-0
il
OH
Reagents: i, SO:-; ii, 2H; iii, CNCl
Scheme 3
complex chain-branching mechanism involving an energy chain in vibrationally excited (CN), must be introduced to rationalize the experimental results.
As a prerequisite to the development of a rapid and accurate method for the
estimation of thioureas and their derivatives, the reactions of CNBr and CNI
with various thioureas have been investigated;422
the molar ratios of the products have been tabulated.
4zr
421
P. J. Kayes and B. P. Levitt, J.C.S. Faraday I , 1973, 69, 1415.

R. C. Paul, R.K.Chauhan,and R. Parkash, Indian J . Chern., 1973,11,380.
286

The U.V. photoelectron spectrum (U.P.S.) of NaCN has been measured
using a He (XI) source.423Of the six bands observed, one could be attributed
to the Na 2p orbital, four to the CN molecular orbitals, and one to the presence of K+ impurity (Table 24). Extended Huckel, CNDO, INDO, and ab
photoelectron spectra of NaCN
Table 24 U.U.
I.P./eV
exptl.
I.P.leV
theor. (ab initio)
5.28
8.96
12.76
16.98
24.67
30.52
4.40
4.75
8.25
24.73
Assgnment
CN-,,
CN-,
CN-2a
K+ impurity
CN-I,
Na-2,
initio MO calculations were carried out on the CN- anion. Peak assignments
were advanced on the basis of these calculations (Table 24). Although the
agreement between the various calculations is but moderate, the ordering of
the CN- anion molecular orbitals can be seen to be the same for all of the
calculations; the ab initio calculations give the best determination of the
energy levels of the CN- anion.423The i.r. spectra of matrix-isolated NaCN
and KCN in Ne, Ar, Kr, and N, matrices have been examined over the
range 3 3 4 0 0 0 cm-1.424 The effect of temperature cycling, which normally
results in the migration of trapped molecules with the generation of polymeric
species, has been pursued. It has been possible to identify the bands in the
spectrum due to both monomeric and polymeric species. Bands due to
sodium or potassium cyanates, thought to be produced in the reaction:
MCN
+ COa -+
MNCO
+ CO
were also identified in some of the systems.

The results of a neutron-diffraction study of a single crystal of cubic
NaCN have given rise to an average C=N bond distance of 1.18
The
high-pressure, high-temperature phase KCN (111) has been shown to be
cubic, probably with space group Pm3rn, and a, = 3.801 f 0.0lOA at
100 *C and 30 kbar.426
The gaseous molecule EuCN has been observed in a high-temperature
mass spectrometer and its atomization energy determined to be 283 f 8
kcal m01-l.~~'Assuming the C-N bond energy to be the same as that of
gaseous CN (178 kcal mol-l), the bond energy D(Eu-CN) is derived as
105 kcal mol-l. This quite high value suggests a sizeable ionic contribution to
the bond energy.
423
484
446
486
W. H. Morrison and D. N. Hendrickson, Inorg. Chem., 1972, 11,2600.

Z. K. Ismail, R. K. Hauge, and J. L. Margrave, J. Mol. Specrroscopy, 1973,45,304.
J. M. Rowe, D. G. Hinks, D. L. Price, and S. Susman, J. Chem. Phys., 1973,58,2039.
P . W. Richter and C. W. F. T. Pistorius, Acta Crust., 1972, B28, 3105.
D. L. Cocke, K. A. Gingerich, and J. Kordis, J.C.S. Chem. Comm., 1973, 561.
287
Surprisingly few reports of the chemistry of C-N ring compounds have
been described within the period of this Report. A synthetic route to symtriazine has been described, however, which yields substantial quantities of
high-purity
The route is a modification of the original method of
Hinkel and Dunn, the sym-triazine being synthesized from HCN and HC1.
The absorption spectra of C3N3H3and C,N3D3 are also reported.42sThe
has been
gas-phase spectrum of cyanuric chloride, 1,3,5-trichloro-s-triazine,
studied in a modified hot-cell assembly;429from an analysis of the spectra
some information on the vibrational character of the molecule has been
obtained. The electronic structure of s-tetrazine, measured by U.V.photoelectron spectroscopy, has been interpreted by means of Rydberg transitions
observed in an electron-impact energy-loss spe~trometer?~~
The lowest I.P.
corresponds to ionization of a lone-pair electron with bonding properties; no
other orbitals can be classified as lone-pair orbitals.
Cyanates and ReZuted Species. Theoretical calculations of the electronic
spectrum of a number of isocyanates HNCO, FNCO, ClNCO, and LiNCO
have been performed by means of semi-empirical MO
The
NCO group is found to be non-linear, in agreement with recent experimental
r e ~ u l t s . 4The
~ ~ results of these calculations have also been used to assign the
U.V. photoelectron spectra of isocyanic acid (WNCO).432A theoretical analysis
of the vibrations of co-ordinated isocyanate (NCO-) and fulminate (CNO-)
groups has been carried out;433the changes in the stretching vibrational
frequency of these groups in metal co-ordination compounds have been
explained,
The matrix-isolated spectra of HNCO, DNCO, HNCS, and DNCS
~ ~of the CNO- anion in the i.r. (550-5000
in the far4.r. (10-50 ~ r n - 9and
cm-1)435have been recorded. The acid molecules were isolated in both argon
and nitrogen matrices at 13 K;434although no absorptions attributable to the
guest molecules were observed in the nitrogen matrix, intense bands were
recorded in the argon matrix. These bands are best explained by rotation of
the molecule about an axis close to the axis of least inertia. Isotopically
enriched cyanate anions have been prepared by direct oxidation reactions and
introduced into KCl and KBr single crystals to a maximum concentration of
ca. 5 wt.%.435The i.r. spectra of the resultant cyanate ion isotopic species
show that these ions are dissolved in the form of a solid solution.
428
42B
430
431
432
433
434
435
E. R. Bernstein and R. E. Smalley, J. Chem. Phys., 1973, 58, 2197.

H. W. Wilson, J. Chem. Phys., 1973, 58, 2663.
L. Fridh, L. Asbrink, BO. Jonsson, and E. Lindholm, Internat. J. Muss. Spectrometry Ion Phys., 1972, 9, 485.
B. M. Rode, W. Kosmus, and E. Nachbaur, Chem. Phys. Letters, 1972,17, 186.
W. Kosmus, B. M. Rode, and E. Nachbaur, J. Electron Spectroscopy, 1973,1,408.
A. Yu. Tsivadze, Yu. Ya. Kharitonov, and G . V. Tsintsadze, Rum. J . Inorg. Chem.,
1972, 17, 1417.
J. A. Cugley and A. D. E. Pullin, Chem. Phys. Letters, 1973, 19, 203.
D. F. Smith, J. Overend, J. C. Decius, and D. T. Gordon, J. Chem. Phys., 1973, 58,
1636.
288

Two groups of authors have studied the i.r. and Raman spectra of single
crystals of potassium t h i o ~ y a n a t e ~as
~ ~a. ~
function
~
of temperature; thus,
whereas Iqbal et aZ.436recorded the spectra over the temperature range
90450 OC, the upper temperature limit of Dao and W i l k i n ~ o n sinvestiga~~~
tion was 300 K. The latter workers observed most of the lattice vibrations of
the crystal and attempted to assign the bands on the basis of group-theory
a r g ~ m e n t s . 4Iqbal
~ ~ et aZ.436also observed pronounced changes in the spectra
as the temperature was increased above the A-phase transition temperature of
KNCS (413 K); these changes were related to the loss of local order and the
emergence of dynamic disorder near the transition temperature.
The construction of the thiocyanate anion in the NH,NCS structure has
been refined from X-ray diffraction data;438the appropriate molecular parameters are r(S-C) = 1.63A, r(C-N) = 1.15A, LSCN = 180. The
presence of N - * H - - - N hydrogen bonds of 2.94 and 3.03 A in this
structure has also been established.438
E.s.r. studies of the effect of radiation on cyanate and thiocyanate anions in
alkali-metal halide crystals and in aqueous glasses have been undertaken.43g
Irradiated crystalline sodium or potassium cyanate at 77 K has e.s.r. spectra
which could be assigned to the radicals N2CO- and NC02-; in contrast,
aqueous glasses containing these salts gave, on irradiation, spectra which
could be interpreted in terms of trapped nitrogen atoms and HCNO- radicals
Potassium thiocyanate had an e.s.r. spectrum after irradiation which has been
interpreted in terms of the dimer anion (NCS)2, well known in pulse-radiolysis studies, and the anions NCS2-. The radical (NCS)r is assigned a o*structure on the basis of its 33S hyperfine tensor components; the radical
NCS2-, like NC02-, is shown to be strongly bent by analysis of its 13C
tensor components. Aqueous glasses gave mainly HCNS- at 77 K, which is
magnetically very similar to HCNO-; nitrogen atoms were not detected. The
radicals CNO and CNS were not positively identified in these studies although
their formation could not be ruled out.
S ~ h r i v e r ~has
~ ~made
* ~ ~a ldetailed study of the dimerization of thiocyanate
anions. It was observed that under conditions of constant acidity the quantity
of thiocyanic acid which can be extracted from solution by methyl isobutyl
ketone decreases with increase of thiocyanate concentration. This has been
interpreted by the formation of dimeric thiocyanate ions according to the
equilibrium:
2SCN-
+ (SCN)i-
The equilibrium has been studied as a function of both ionic and acid
strengths; it is concluded that the results, although dependent on ionic
436
Z. Iqbal, L. H. Sharma, and K. D. Moller, J. Chem. Phys., 1972, 57,4728.
437
N.Q. Dao and G . R. Wilkinson, J. Chem. Phys., 1973,59, 1319.

V. E. Zavudnik, Z. V. Zuonkova, G. S. Zhdanov, and E. G. Mievich,
438
Cryst., 1972, 17, 85.

4s9 I. S. Ginns and M. C . R. Symons, J.C.S. Dalton, 1973, 3.
440 L. Schriver, Bull. SOC.chim. France, 1973, 1882.
441 L. Schriver, Bull. SOC.chim. France, 1973, 1884.
Soviet Phys.
289
strength, are not modified by the nature of the cation present in the aqueous
phase and that dimerization will only occur in slightly acidic solution.
A study of the kinetics of thereaction between thiocyanate anions and iodine
in aqueous solutions at constant pH values has established that the oxidizing
agent is hypoiodous acid (HIO);442it is thus concluded that the initial reaction
is:
NHdSCN
H I 0 --+ NHICNS-0 + HI
the intermediate rapidly reacting with iodine to yield H2S04and HI according
to the process:
NH4CNS=0
+ 312 + 4H20
NH40CN
+ 6HI + H 2 S 0 4
The products of the reaction of sulphur dicyanide S(CN)2with the thiocyanate anion include yellow materials of low solubility in water, S(CN)2,nH,O; SCN-; HCN; H+; SO$-; and HOCN;443the rates of reaction and the
products are consistent with the formation of (SCN), as an intermediate.
An ultrasonic study of the solvation of inter alia potassium thiocyanate in
DMF has shown the solvation number of the solute to be one;444this is in
accord with the formation of a solute-solvent complex involving one mole of
each constituent.
The thermal decomposition of copper thiocyanate~:~~
copper halide
t h i o ~ y a n a t e s and
, ~ ~ platinum chloride t h i o c y a n a t e ~
has
~ ~been
~ the subject of
two papers in the Russian literature. The first stage in the thermal decomposition of the copper halide thiocyanates is a detachment of the thiocyanatogroup to give the copper(1) halide (in the absence of air) or copper(r1)
Decomposition of copper(1) thiocyanate involves disproportionation of the
ligand, the first stage in the process yielding the compound Cu,S(CN),,
which has been isolated and studied by physicochemical methods.445The
decomposition of copper(I1) thiocyanate follows that of the copper halide
thiocyanates, a thiocyanato-group being split off and the monothiocyanate
being produced.445
The phase relationships associated with a number of aqueous systems
involving thiocyanates have been investigated; the results obtained are
summarized in Table 25.447461
442
44s
444
445
4413
447
448
449
460
461
A. I. Morozov, M. S. Sytilin, and I. A. Makolkin, Russ. J. Phys. Chem., 1972, 46,

1324.
D. F. Merr and I. R. Wilson, J.C.S. Dalton, 1973, 459.
C. V. Chaturvedi and S. Parkash, Indian J. Chem., 1972, 10, 669.
S. S. Batsanov and E. N. Zalivina, Russ. J. Inorg. Chem., 1972, 17, 161.
S. S. Batsanov, P. N. Kuznetsov, and E. D. Ruchkin, Rum. J . Inorg. Chem., 1972,17,
168.
P. S. Bogoyavlenskii and E. D. Gashpur, Russ. J. Inorg. Chern., 1972, 17, 1607.
2. G. Karev, I. N. Lepeshkov, and E. I. Kukulieva, Russ. J . Imrg. Chem., 1972, 17,
267.
R. Turgunbekova, K. Nogoev, and K. Sulaimankulov, Russ. J . Inorg. Chem., 1972,
17, 753.
R. Turgunbekova, K. Nogoev, and K. Sulaimankulov, Russ. J . Inorg. Chem., 1972,
17, 1046.
R. Turgunbekova, K. Nogoeva, and K. Sulaimankulov, Russ. J. Inorg. Chem., 1972.
17, 754.
290
Table 25 Phase relationships in aqueous systems containing thiocyanate anions
Systenz
KHCOS-KS CN-H20
Na2Mo04-NaSCN-H,O
CO(NH2)2-KSCN-H20
CO(NH,),-Mg(SCN)2,HzO
CO(NH2)2-Ca(SCN)2-H20
Compounds present
Ref.
447
448
449
450
KSCN,CO(NH&
Mg(SCN),,8CO(NHz),;
Mg(SCN)2,4CO(NH2)z
Ca(SCN),,4CO(NH2),
451
2 Silicon, Germanium, Tin, and Lead

Hydrides of Silicon, Germanium, Tin, and Lead.-The synthesis of silyl,
germyl, and stannyl analogues of saturated hydrocarbons has received
significant attention during the past year. Stannane is produced in yields of
up to 47% by the sodium tetrahydroborate reduction of tin(@ or tin(1v)
chlorides in aqueous media.452 In the presence of a primary or secondary
amine, germylcyclopentadiene, C,H,GeH,, decomposes to give a mixture of
digermane (ca. 20A and trigermane (ca. 45 %), from which the latter is
easily separated by fractionation. Ammonia and triethylamine caused only
very slow d e c o m p ~ s i t i o n .Feher
~ ~ ~ has synthesized linear and branched
oligosilanes containing from three to seven silicon atoms by the acid decomposition of magnesium silicide followed by preparative gas chromatography. Many physicochemical data for the compounds were reported,
including lH n.m.r. spectra.454The potassium-silyl compounds K-SiH(SiH3)2,K-Si(SiH,),,
and K-Si(SiH,),(Si,H5)
react with phenylchlorosilane
to give phenylisotetrasilane, phenylneopentasilane, and phenylneohexasilane,
respectively. The phenyl groups are readily cleaved by HBr at -80 O C to yield
the corresponding bromo-isotetrasilane, -neopentasilane, and -neohexasilane,
which may then be reduced by LiAlH, to the unsubstituted ~ i l a n e s .Neopen,~~
tasilane, which is the only isomer not found in sufficient amounts after acid
hydrolysis of magnesium silicide, has also been prepared by the passage of a
silent electric discharge through a mixture of mono- and d i - s i l a n e ~The
.~~~
HBr cleavage of phenyl groups from silicon followed by reduction of the
resultant bromosilane has been used successfully by Hengge to synthesize
cyclopentasilane, the first example of an unsubstituted silicon h~dride,4~
as shown in Scheme 4. Asymmetric disilanes have also been prepared by
similar methods from trimethyltriphenyldisilane.Stepwise cleavage of phenyl
groups by HI occurs, but Faeduction to MgSiSiH,Ph is necessary before the
last phenyl group can be removed. Treatment of the resultant Me3SiSiH21
4az
453
452
455
460
467
A. D. Zorin, I. A. Frolov, and T. V. Morozova, J . Gen. Chem. (U.S.S.R.),

1972,42,
890.
P. C. Angus and S. R. Stobart, J.C.S. Chem. Comm., 1973, 127.
F. Feher, P. HBdicke, and H. Frings, Znorg. Nuclear Chem. Letters, 1973, 9, 931.
F. Feher and R. Freund, Inorg. Nuclear Chem. Letters, 1973, 9, 937.
F. Hofler and R. Jannach, Inorg. Nuclear Chem. Letters, 1973, 9, 723.
E. Hengge and G . Baur, Angew. Chem. Znternat. Edn., 1973, 12, 316.
291
Ph2SiSiPhz
I
I
PhzSi, , + 3 i P h 2
Ph2
Br2Si-SiBr2
Br2Si,si, SiBr2
Br2
ij
H2Si-SiH2
H2Si,Si, SiH2
H2
Reagents: i, HBr; ii, LiAIH4 .
Scheme 4
with methanol yields Me,SiSiH,(OMe), which decomposes at

afford a mixture of products458as shown in Scheme 5 .
> 120 'C
to
Me3SiSi12Ph A Me3SiSiHzPh
Me3SiSiPh3
Me3SiSiH2(OMe)
li
Me3SiSiH21
1 2 0 Y
Me3SiSiH3
+ Me3SiSiH2(Me) + Me3SiSiH(OMe)z+ Me3SiSi(OMe)3
Reagents: i, HI; ii, LiAlH4; iii, MeOH
Scheme 5
Iodine cleaves germane and C2H4]germane to give GeH,I and GeD,I,

respectively.459Silicon-hydrogen bonds of fluorosilanes are cleaved by phenols, affording a useful preparation of aroxyfluor~silanes.~~~
The alcoholysis of
diarylsilanes (Scheme 6) and hydrosilylation of carbonyl compounds (Scheme
R&H2
+ R20H A
RiSi
/H
+ H2
'OR2
Scheme 6
7) are effectively catalysed by chlorotris(triphenylphosphine)rhodium(I) and

dichloro(triphenylphosphine)ruthenium(II), providing a selective route to
diarylalkoxysilanes.4"' A variety of dihalogenodiphosphinenickel(rr) comRfSiHz
+ R2R3C=0
RiSi(H)OCHR2R3
Reagents: i, catalyst (5 X low4mol l-l),C6H6, 20-70
"C
Scheme 7
plexes also effectively catalyse the hydrosilylation of alkenes and alkynes.

The reactions do not appreciably proceed below 90 'C, but at 120 O C reaction
468
460
ldl
20
E. Hengge, G . Bauer, and H. Marketz, 2. anorg. Chem., 1972, 394, 93.

J. W. Anderson, G . K. Barker, J. E. Drake, and R. T. Hemming, Synth. Inorg.
Metal-Org. Chem., 1973, 3 , 125.
G. Schott, P. Schneider, and H. Kelling, 2. anorg. Chem., 1973, 398, 293.
R. J. P. Corriu and J. J. E. Moreau, J.C.S. Chem. Comm., 1973, 38.
292
proceeds smoothly to yield in many cases an abnormal product arising from
hydrogen-chlorine interchange on silicon besides the expected normal
product. The reactivity of the silicon hydrides decreases in the order HSiCl,
> HSiMeC12 > HSiMe,Cl, >> HSiMe3.462*463
A comparison of the catalytic
activity in hydrosilylation of the ethylene-nickel(o) complexes 1,2bis(dipheny1phosphino)ethane-(ethylene)nickel(o)
and bis(tripheny1phosphine)(ethylene)nickel(o) with that of the corresponding nickel(@ complexes
dichloro-1,Zbis(diphenylphosphino)ethanenickel(r~) and dichlorobis(triphenylphosphine)nickel(rI) shows that the reaction profiles are similar, but
that the nickel(r1) catalysts require a much longer induction period.
A mechanism involving nickel(o) species is proposed for the hydros i l y l a t i ~ n The
. ~ ~ hydrosilylation
~
of alkenes catalysed by nickel (11) chloride
complexes with 1,2-bis(dimethylphosphino)-l,2-dicarba-cZoso-dodecaborane
produces both terminal and inner adducts in comparable
Oxidative addition of M-H bonds to Vaskas compound, trans-carbonylchlorobis(triphenylphosphine)iridium(I), occurs with SiH,X (X = H, Cl,
Br, or I) and with GeH, in benzene at room temperature to give insoluble 1 :1
adducts. With germyl halides GeH,X (X = C1, Br, or I) and digermane,
initial reaction gives soluble 1 :1 adducts, whose stereochemistries are determined from their n.m.r. spectra, but after a short period insoluble adducts
precipitate. The reaction with disilane is more complex, no single product
being obtained. On prolonged standing with excess silyl chloride, Vaskas
compound gives dichlorosilane and a soluble silyl complex of six-co-ordinate
iridium containing two Ir-H bonds.465Rankin has studied the reactions of
the silyl and germyl chalcogenides (MH,),X (M = Si or Ge; X = 0,S,
Se, or Te) with chloro- and bromo-difluorophosphine using n.m.r. spectroscopy. With PF,Br, reaction occurs at room temperature with the sulphides,
selenides, and tellurides to give MH,XPF,, (PF,),X, and MH3Br.466The
silyl compounds (H3Si)2X (X = 0, S , or Se) and (H,Si),Y (Y = P or As)
react with methyl-lithium in ether at low temperature to afford the colourless
crystalline lithium salts LiXSiH, and LiY(SiH,),, respectively. The sulphur
and selenium salts react with trimethylchlorosilane to give the mixed compounds, H3SiXSiMq.467Chlorosilane undergoes condensation reactions
with chloromethylchlorosilanes, to form methylene bridges between silicon
atoms:
ClCH,MeSiCl,
462
+ 2HSiC1, + C1,SiCHaSiMeC1, + Sic& + H2
Y. Kiso, M. Kumada, K. Tamao, and M. Umeno, J. Organometallic Chem., 1973,50,

297.
Y . Kiso, M. Kumada, K. Maeda, K. Sumitani, and K. Tamao, J. Organometallic

Chem., 1973,50, 311.
464 M. Kumada, K. Sumitani, Y. Kiso, and K. Tamao, J. Organometallic Chem., 1973,
50, 319.
46i5 E. A. V. Ebsworth and D. M. Leitch, J.C.S. Dalton, 1973, 1287.
466 D. E, J. Arnold, J. S. Dryburgh, E. A. V. Ebsworth, and D. W. H. Rankin, J.C.S.
Dalton, 1972, 2518.
487 S. Cradock, E. A. V. Ebsworth, H. Moretto, D. W. H. Rankin, and W. J. Sacage,
Angew. Chem., 1973, 85, 344.
4G3
293
The condensation reactions are usually accompanied by some disproportionation of the c h l o r o ~ i l a n e sCobalt-60
.~~~
7-ray irradiation of mixtures of digermane and ethene produces a mixture of ethylmono- and ethyldi-germanes,
from which the latter compound is readily separated by f r a c t i o n a t i ~ n . ~ ~ ~
Triorgano-silicon, -germanium, and -tin hydrides R,EH (E = Si, Ge, or
Sn) react with the chromium carbene complex Cr(CO), [C(OMe)Ph] in
pyridine to give the insertion products R,ECH(OMe)Ph. On the basis of
kinetic data, the mechanism in Scheme 8 is proposed.470Reactions with
(CO)5Cr-C(OMe)Ph
slow
-0Me
/
(C0)sCr- -,-,C,Ph
H--------*-ER~
c-
p,,,
-R8ECH(OMe)Ph
fast
Scheme 8
similar molybdenum and tungsten carbene complexes in the presence of

pyridine or acetonitrile in hexane showed that the rate of reaction varied with
the metal in the order Mo >> Cr > W, and with the metal hydride in the
order Et,SiH > Ph,SiH < Ph,GeH < Ph,SnH,Pr,SnH.471
Weak complex formation occurs between triethylamine and mono-, di-,
and tri-silanes. The Lewis acidity increases with increasing chain length of the
silane. Dimethylamine does not react with disilane, but the latter compound
together with HaSiNMe2 is produced with trisilane. Deuteriation studies
suggest the following mechanism, in which the disilanyl group functions in the
same way as a halogen:472
Potassium germyl, KGeH,, and trimethylborane react at 0 OC in diglyme to

give the adduct KGeH,BMe,. Quenching with water after 1 minute produced
germane as the major hydrolysis product:
GeH,BMe;
+ H,O
GeH,
+ HOBMe
E. A. Batyaev and N. P. Kharitonov, J . Gen. Chem. (U.S.S.R.),

1973,43,446.
J. K. Kandelwal and J. W. Pinson, Znorg. Nuclear Chem. Letters, 1973, 9, 393.
470 J. A. Connor, J. P. Day, and R. M. Turner, J.C.S. Chem. Comm., 1973, 578.
471 J. A. Connor, P. D. Rose, and R. M. Turner, J . Organometallic Chem., 1973,55, 111.
m J. J. Watkins, M. D. Sefelk, and M. A. Ring, Znorg. Chem., 1972, 11, 3147.
468
469
294
Quenching after longer periods produced relatively large amounts of hydrogen

and digermane, that were presumably due to the disproportionation of the
GeH,BMe; ion, ~ i z . 4 ~ ~
2GeH,BMe,
HBMe,
+ Ge,H,BMe;
The pyrolysis of silylphosphine, SiH,PH2, in the presence of Me2SiD2

(stable at 400 "C) demonstrates that decomposition takes place by the steps
(79) and (80). The ratio kJk2 = 2.6. The biradicals :SiH2 and :PH subseSiH3PH2
kl
:SiH,
+ PH,
k-1
SiH,PH2
kz
+
SiH4 +
:PH
k-2
quently insert into the Si-D bond of MezSiD2,forming MezSi2H2D,(presumably Me2SiDSiH2D)and Me2SiPHDz (presumably Me,SiDPHD). The
pyrolysis of GeH,SiH, in a 1 O : l excess of MeSiH, and MeSiD, (stable at
500 "C) shows that decomposition takes place by equations (81) and possibly
GeH,SiH,
+ SiH4 + GeH,
(8 1)
GeH3SiH,
+ SiHz + GeH,
(82)
by (82), but not by Si-H, Ge-H, or Si-Ge bond fission.474

Several papers have reported investigations into the reaction of silanes
with radical species. Strausz has measured absolute rate constants for hydrogen abstraction by deuterium atoms from SiH,, Si2H6, and Me,SiH,-,
(n = 1-3) at room temperature in competition with ethene. The silanes
were more reactive than their hydrocarbon counterparts and have reactivities
of the same order of magnitude as that of ethene, in the order Si2H6> Me,SiH > MezSiH2> MeSiH, > SiH4.475Arrhenius parameters have also been
determined for the hydrogen-transfer reactions of methyl, ethyl, n-propyl,
and isopropyl radicals with silane, disilane, and m e t l i y l s i l a n e ~ .Hydro~~~*~~~
gen-atom abstraction from SiH,Cl by 'CF, radicals has been studied in the
temperature range 69-168 O C . At 400 K, the rate constant for the reaction
'CF, SiH,CI is 3.6 times greater than the average value reported for
SiHC1,.478
CF,
The decomposition of chemically activated dimethylsilane and ethylsilane
produced by the reaction of singlet methylene with methylsilane has been
+
+
473
474
476
476
47 7
478
E. R. De Staricco, C. Riddle, and W. L. Jolly, J . Inorg. Nuclear Chem., 1973, 35,

297.
L. E. Elliott, P. Estacio, and M. A. Ring, Inorg. Chem., 1973, 12, 2193.
K. Obi, H. S. Sandhu, H. E. Gunning, and 0. P. Strausz, J. Phys. Chem., 1972, 76,
391 1.
R. E. Berkley, I. Safarik, H. E. Gunning, and 0. P. Strausz, J . Phys. Chem., 1973,
77, 1734.
R. E. Berkley, I. Safarik, 0. P. Strausz, and H. E. Gunning, J. Phys. Chem., 1973,
77, 1741.
N. L. Arthur and B. R. Harman, Austral. J. Chem., 1973,26, 1269.
studied, and the mechanisms of equations (83)-(87)
been proposed.479
and (88)-(92)
295
have
+ MeSiH,
+ CHI + MeSiH
Me,Si: + Ha
MeaSiH* + H'
Me2SiHt + Me'
3
+=
4 Me,SiH2
CH,CHzSiH:
+ 'SiH,
+ HI
CHsCH2SiH2 + H'
+ CaHB+ :SiH2
3
CH,CH;
CH,CH2SiH
+=
W
---+
CH,CH,SiH,
The room-temperat ure mercury 6vP1) photosensitization

produces H2, SiH,, Si&,, Si,Hlo, and a solid deposit. Mechanistic studies
show that the sole primary step is:
Hg6(3P1)
+ SipH,
Hg
+ HSi2H6
Q.' w 1.0
The hydrogen atoms produced may then react with disilane in two ways:
+ siaH6\
+ SiHs
cp = 0.34
+ SisH6
cp = 0.66
SiHd
H,
Further reactions of the mono- and di-silyl radicals account for the observed
products.480Product studies on reactions of recoiling germanium atoms in
germane, digermane, and germanesilane mixtures support a mechanism in
which 76GeH4is an important intermediate, giving rise to a next higher
homologue of the substrate and also to products of unimolecular decomposition of the higher homologue. Complete mechanisms are suggested for
germanium atoms recoiling in germane and germane-silane mixtures.481
Similar studies of recoiling silicon atoms in silane have been carried out and
mechanisms proposed.4e2 Endothermic ion-molecule reactions in silane
have been investigated. Si$ is observed only from endothermic reactions of
Sit and SiHz with silane. Endothermic as well as exothermic channels are
observed for the formation of Si2Hf, Si2H$, and Si2Hg?83Ion-molecule
47B
480
481
483
483
W. L. Hase, C. J. Mazac, and J. W. Simons, J. Amer. Chem. SOC.,1973, 95, 3454.

T. L. Pollock, H. S. Sandhu, A. Jodhan, and 0. P. Strausz, J. Amer. Chem. SOC.,1973,
95, 1017.
P. P. Gaspar and J. J. Frost, J. Amer. Chem. SOC.,1973, 95, 6567.
G. W. Stewart, J. M. S. Henis, and P. P. Gaspar, J . Chem. Phys., 1973, 58, 890.
J. M.S. Henis, G. W. Stewart, and P. P. Gaspar, J. Chem. Phys., 1973, 58, 3639.

reactions occurring in ionized silane have also been studied by high-pressure
mass spectrometry.484Bimolecular self-reaction is the dominant pathway
for the disappearance of silyl and trimethylsilyl radicals dissolved in the
corresponding ~ i l a n e . ~ ~ ~
The kinetics of the gas-phase reaction between iodine and trimethylsilane
have been investigated. Analysis of the products shows that hydrogen abstraction is the sole occurring process. The value of the bond-dissociation
energy D(Me,Si-H),
376 kJ mol-l (90 kcal mol-l), calculated from the
experimental data is considerably higher than previous estimates.486The
Si-D bond-dissociation energies in Me,SiD,,
(n = 1-3) are estimated to
be considerably less than this value from the relative yields of DT per Si-D
bond for the abstraction of D by recoil tritium atoms.487An upper limit of
87 kcal mol-l for D(H,Si-H)
has been estimated from the reaction of
fluorine atoms with silane.48s
Accurate frequency measurements of the pure rotational lines in germane
have been determined.489The microwave spectra of trimethylgermane490and
of germyl bromide in excited vibrational states491have been recorded. For
trimethylgermane, using an assumed structure for the methyl group, the
following structural parameters were determined: r(Ge-H) = 1.532 f
0.001 A, r(Ge-C) = 1.947 f 0.006 A, LCGeH = 109.3 f O:1.490 The i.r.
spectra of ClCH,SiH3, ClCH2SiD3, BrCH,SiH,, BrCH,SiD,, ClCH,GeH,,
and ClCH,GeD, for both the gaseous and solid states in the region 4000-250
cm-l have been obtained and normal modes assigned. Force constants have
been calculated using a modified Urey-Bradley force field.492The force
fields, frequencies, Coriolis constants, and centrifugal distortion constants
for compounds of the type GeH,X and GeD,X (X = Me, CN, or C=CH)
have been calculated.493
The reaction SiH, H- 3 SiHF has been investigated by employing ab
initio quantum-chemical techniques. With respect to silane and hydride ion ,
a trigonal-bipyramidal form of SiH: is found to be stable by 16.9 kcal mol-l,
and a tetragonal-pyramidal form by 14.0 kcal mol-l. Furthermore, the
attack of hydride ion on silane is found to proceed with the hydride ion
approaching a face of the tetrahedron of silane with an activation energy of
8.6 kcal mol-l. Conformational equilibria of SiH,,X, species (X = strongly
electronegative substituent) have also been studied.494 Statistical OCEcalculations have been reported for the ground-state energies and bond
296
T.-Y. Yu, T. M. H. Cheng, V. Kempter, and F. W. Lampe, J. Phys. Chem., 1972,76,

3321.
485 P. P. Gaspar, A. D. Haizlip, and K. Y. Choo ,J. Amer. Chem. SOC.,1972,94, 9032.
486 R. Walsh and J. M. Wells, J . C . S. Chem. Comm., 1973, 513.
487 A. Hosaka and F. S. Rowland, J. Phys. Chem., 1973, 77, 705.
48* W. H. Duewer and D. W. Setser, J. Chem. Phys., 1973, 58, 2310.
489 A. Rosenberg and I. Ozier, J. Chem. Phys., 1973, 58, 5168.
4g0 J. R. Durig, M. M. Chen, Y. S. Li, and J. B. Turner, J. Phys. Chem, 1973,77, 227
4B1 L. C . Krisher and S. N. Wolf, J . Chem. Phys., 1973, 58, 396,
492 K. Ohno and H. Murata, Bull. Chem. SOC.Japan, 1972, 45, 3333.
493 V. N. Yarandina and L. M. Sverdlov, Russ. J . Phys. Chem., 1973, 47, 153.
4g4 D. L. Wilhite and L. Spialter, J. Amer. Chem. Soc., 1973, 95, 2100.
484
297
distances of the hydrides MH, (M = C, Si, Ge, Sn, or Pb). The results
obtained are in good agreement with experimentally determined values.
Those for PbH, are reported for the first time.495 Bond orbital and
SCF-LCAO-M049s and one-centre H a r t r e e - F ~ c kcalculations
~~~
have been
performed on methane and silane.
The highest-energy orbital of phenylsilane appears to be stabilized compared to that in toluene, apparently due to ( p - 4 ) bonding.498
~
The 29Si-{1H)
nuclear Overhauser effect is substantial for Ph,SiH but small for PhSiH,.
The difference is attributed to the low barrier to internal rotation about the
Si-C bond in p h e n y l ~ i l a n e The
. ~ ~ ~electron-impact-induced ionization and
dissociation of CH, and SiH, have been studied using quadrupole mass
spectrometry.500The principal thermodynamic functions of stannane have
been calculated for the temperature range 298.15-6000 K.501The separation
of silicon isotopes by the thermal diffusion method has been studied using
silane and silicon t e t r a f l ~ o r i d e . ~ ~ ~
Halides of Silicon, Germanium, Tin, and Lead.--Synthesis. Several papers

report further investigations into the 'direct' synthesis of chloro-silanes,
-germanes, and -stannanes. Studies of the interaction of methyl radicals with
HSiCl,, MeSiCl,H, MeSiCl,, and Me2SiC12lead to the conclusion that the
direct synthesis of methylchlorosilanes proceeds very likely by a chemisorption mechanism, possibly accompanied to a very small extent by a free-radical
mechanism.503Various aspects of the synthesis have been studied by Russian
investigators. Chlorination of silicon at ca. 35OoC prior to reaction with
methyl chloride lowers the starting temperature of the reaction to ca. 300 "C.
However, reaction of the chlorinated silicon with methyl chloride results in
loss of activity by the surface from consumption of intermediate products
formed there during chlorination. The activity is restored by further treatment
with chlorine.504Activation energies for the breakdown of methyl chloride on
a siliconxopper alloy, pure silicon, and technical silicon have been estimated
to be 14.9, 44.0, and 24.2 kcal mol-l, respectively. The breakdown on the
alloy is substantially accelerated if the surface is first treated with hydrogen
chloride at 280-300C. In the breakdown over the alloy, the chlorine is
completely bound on the surface during the induction period in forms
including compounds of the type (SiCl)n,whose presence is necessary for the
495
498
499
503
K. Hensen, M. Achatz, and R. Miiller, Theor. Chim. Acta, 1973, 28, 297.
S. Kohda and S. Katagiri, Bull. Chem. SOC.Japan, 1973, 46, 1428.
P. W. Deutsch and A. B. Kunz, J . Chem. Phys., 1973, 59, 1155.
R. A. N. McLean, Canad. J . Chem., 1973, 51,2089.
R. K. Harris and B. J. Kimber, J.C.S. Chem. Comm., 1973, 255.
J. D. Morrison and J. C. Traeger, Znternat.J . Muss Spectrometry Ion Phys., 1973, 11,
289.
Yu. A. Shishkio, V. V. Marusin, and A. N. Kolyshev, Russ. J . Phys. Chem., 1973,
47, 404.
Y.Ando and T. Tokuda, Z . phys. Chem. (Frankfurt), 1973, 83, 153.
J. Joklik and V. Bazant, Coll. Czech. Chem. Comm., 1972, 31, 3772.
V. I. Zubkov, S. A. Golobtsov, K. A. Andrianov, and M. V. Tikhomirov, Zzuest.
298

start of chloromethylsilanes.505The products from ethyl chloride and various
copper-silicon catalysts have also been studied for the initial stages of
reaction. In the induction period, CuCl, HCI, H2, C,H4, and apparently
(SiCl), are formed. The introduction of calcium silicide into the Si-Cu mass
increases the decomposition of ethyl chloride, but the amount of CuCl and
(SiCl), declined greatly.506X-Ray diffraction and chemical analysis show that
when calcium is fused into Cu,Si silicon-copper alloys, calcium disilicide,
free copper, and silicon-copper phases with a lower copper content are
formed. After treatment of the specimens with ethyl chloride at 350 OC, the
calcium disilicide phase could no longer be detected in the Si-Cu-Ca alloys,
but it is almost completely converted into calcium chloride only 30 minutes
after the start of the reaction.507Trace amounts of bismuth sharply inhibit
the decomposition reaction of ethyl chloride with the Si-Cu contact mass to
form EtSiCl, or EtSiHCl,. However, the decomposition in the presence of
BiCl, results in the smooth transfer of chlorine to silicon to form Et,SiC1,.508
The effect of phase composition of the Si-Cu contact mass on the direct
synthesis from chlorobenzene has also been studied. The effect of the addition
of aluminium, calcium, iron, or Group V elements depends on the activity of
the copper catalyst and the presence of promoters (e.g. ZnO, CdCl,) in the
mixture. Group V elements (P, As, Sb, and Bi) which are effective promoters
for the synthesis of alkylchlorosilanes do not activate catalysis mixtures in
similar concentrations in the synthesis of chlorophenylsilanes. The presence of
sodium chloride in concentrations of less than 1 % completely deactivates the
catalysis mixtures.509The effect of the addition of the promoters CdCl and
ZnO to the contact mass is to cause the formation of the Cu,Si phase, the
amount of which roughly correlates with the overall activity of the Cu-Si
mass and with the selectivity of Ph,SiC12 formation.510The effect of the
addition of hydrogen on the reaction of methyl chloride with Si-Cu under
pressure at 320 "Cis to cause an increase in the amount of MeSiHCl, formed
at the expense of Me2SiC12.511The activities of the single-phase alloys
cc(Ge in Cu), [(Cu,Ge), and c(Cu,Ge) in the reaction with methyl chloride to
form methyl-chlorogermanes at 426.7 "C have been studied, and they display
approximately the same reactivity when compared on the basis of the number
605
606
507
608
609
510
611
N. T. Ivanova, L. D. Prigozhina, S. A. Golubtsov, and A. I. Gorbunov, J. Gen. Chem.

(U.S.S.R.),
1972, 42, 1104.
V. V. Moskovtsev, S. A. Golubtsov, K. A. Andrianov, and R. A. Turetskaya, Izvest.
V. V. Moskovtsev, S. A. Golubtsev, E. A. Mikheev, V. G. Kostogonov, and Z. V.
Pastukhova, Russ. J . Phys. Chem., 1973, 47, 153.
V. V. Moskovtsev, S. A. Golubtsev, K. A. Andrianov, N. P. Lobusevich, and L. D.
Prigozhina, Izvest. Akad, Nauk S.S.S.R., Ser. khim., 1973, 870.
R. A. Turctskaya, S. A. Golubtsev, V. G. Dzvonar', and M. A. Luzganova, J . Gen.
Chem. (U.S.S.R.), 1972, 42, 1507.
R. A. Turetskaya, A. A. Slinkin, M. A. Luzganov, S. A. Golubtsev, V. G. Dzvonar',
M. I. Dashevskii, and G. A. Ashavskaya, Izvest. Akad. Nauk S.S.S.R., Ser. khim.
1973, 519.
J. Rathousky, 0. Kruchna, and J. Joklik, Chem. prrimysl, 1 9 7 2 , 2 2 , 4 8 5 (Chem. Abs.
1 9 7 3 , 7 8 , 4 3 573s).
299
of germanium atoms exposed to methyl chloride. Selectivity for Me,GeCl,

approached 100% at 0% conversion of germanium, supporting an ionic
mechanism. Mechanical mixtures of alloys and free germanium showed
greatly enhanced activities.512Cobalt-60 ?-ray irradiation has been used to
promote the reaction between metallic germanium and liquid alkyl halides at
200-240 "C or with gaseous halides at 160-220 "C.Only organogermanium
trihalides could be obtained using higher halides.513
The direct reaction between chloromethylsilanes and Cu-Ge couples at
360-40O"C has been employed by Mironov and Gar to prepare several
mixed organosilicon-germanium compounds, as shown in Schemes 917.514-618
X(CH2XS( + Ge-Cu
X = C1 or Br; n = 1-5
370-380 "C
_____+
X(CH2),GeX3
+ X3Ge(CHz),Ge&
Scheme g514
370-380 "C.
XSiMe2CHzCl Ge-Cu
A (XSiMe2CH2)2GeC12
X = F, OMe, o r OSiMes
Scheme 10514
Cl3SiCHMeCI
+ Ge-Cu
370-380 "C
ClaSiCHMeGeCIs + (Cl&iCHMe)zGeCla
Scheme 11514
ClMelSiCH2Cl
310-390 "C
+ Ge-Cu
(C1MezSiCH2)zGeC12
Scheme 12616
C1
(ClCH2SiMe2)20-t Ge.-Cu
+-
Scheme 13515
sla T. Chong and J. M. Skaates, J. Catalysis, 1973, 28, 20.
s13
V. V. Pozdeev, N. V. Fomina, N. I. Sheverdina, and K. A Kocheskov, Izvest Akad.

Nauk S.S.S.R., Ser. khim., 1972, 2051.
V. F. Mironov, T. K. Gar, and A. A. Buyakov, Zhur. obshchei Khim., 1973,43, 798,
V. F. Mironov, T. K. Gar, and A. A. Buyakov, J. Gen. Chem. (U.S.S.R.),
1972, 42,
&16
T. K. Gar, A. A. Buyakov, and V. F. Mironov, J. Gen. Chem. (U.S.S.R.), 1972,42,
1354.
1512.
A. A. Buyakov, T. K. Gar,and V. F. Mironov, J. Gen. Chem. (U.S.S.R.),1973,43,
623.
*la V. F. Mironov, T. K. Gar, and A. A. Buyakov, J. Gen. Chem. (U.S.S.R.),
1972,42,
2005.
617
300
CW2
Me2Si(CH2C1)2
,CH2GeCH2
Me&
CH2GeCH2
SiMe,
-[Me2SiCH2GeCl2CH2ln-
/\
c1
c1
Scheme 14516
Me3SiCHC12+ Ge-Cu
370-390 C
_____)
c1
C1
Ge/
Me3SiCH
G
e
C1/
\CHSiMe8
C
l
Scheme 15516
O[SiMe(CH2C1),],
+ Ge-Cu
360-370C
c1
c1
\ /
H2C-Ge-CH2
MeSi-0-SiMe
HZC-Ge-CHi
c1 C
l
Scheme 16517
CI,Me3-,SiCI
n = 0-3
C1
+ Ge-Cu
370-400 C
+ CIJL~J-nSiGeC13
[C1,Me3-nSiCH2]2GeC12
Scheme 17518
The reactions of a-chloromethyl ethers ROCH,Cl (R = Me, Et, or Bu)

with powdered tin at 20-80 C afford low yields of the dihalides (ROCH,),SnC1,.519 Dimethyltin dichloride may be prepared in 75-80 % yield by heating
tin with methyl chloride in hexamethylphosphoramide at 140-1 50 C.520
Silicon tetrabromide is obtained by bromination of pure or commercial
silicon, or ferrosilicon, in the presence of Cu, CuBr, or CuBr, at 350-600 C.
A 97 % yield of germanium tetraOptimum yields are obtained at 500 0C.521
chloride is obtained when vitreous germanium dioxide is treated with
6ao
621
V. I. Shiryaev, E. M. Stepina, and V. F. Mironov, Zhur. priklad. Khim., 1972, 45,

2124 (Chem. A h . , 1973, 78,29 950f).
V. I. Shiryaev, E. M. Stepina, V. L. Makhalkina, and V. F. Mironov, Zhur. priklad.
Khim., 1973, 46, 1149 (Chem. Abs., 1973, 79, 42 632 u).
G. N. Khodalevich, L. G. Sakovich, and V. V. Serebrennikov, Zhur. priklad. Khim.,
1972,45, 1863 (Chem. Abs., 1973,78, 51 965m).
301
concentrated hydrochloric acid and the reaction mass subsequently treated
with gaseous hydrogen
The heats of dissolution of metallic tin in
hydrochloric acid solutions of hydrogen peroxide have been measured
calorimetrically at 25 OC,and the enthalpies of formation of SnCI, in these
solutions have been deduced.523The enthalpy changes for the reactions :
Sn(c)
2IdC) 4- 4165CS2(1) + [SnI, :4165CS,](~0l)
SnI,(c)
4223CS2(1) -+ [SnI, :4223CS,](~0l)
at 298.15 K have been determined by solution calorimetry to be -46.7 f 0.3

and +3.2 f 0.1 kcal mol-l, respectively. These values yield a value of
-49.9 f 0.4 kcal mol-1 for the enthalpy of formation of SnI, [AH,"(Sn,;
c; 298 K)].615
Reactions of Silicon, Germanium, and Tin Tetrahalides and Related Compounds.
The equilibrium partial pressures of SiF, have been measured for the reactions:
2Si02(s)
Be,SiO,(c)
+ 2BeFZ(d) + SiF,(g) + Be,SiO,(c)

+ 2BeF,(d) + SiF,(g) + 4Be0
where d denotes BeF, in solution with LiF as molten Li,BeF,.524 H F is selectively absorbed from HF-SiF, mixtures by solid sodium fluoride, thus making
separation of such mixtures possible.525Bromine-iodine exchange between
bromofluorosilanes and HSiI, leads to the new fluoroiodosilanes SiFCI,I,
SiFClI,, SiFBr,I, SiFBrI,, and SiF,BrI, as well as SiFI, and SiF212.526The
fluoroiodosilanesSiF,,I,
( x = 1 or 2) can be prepared by the cleavage of the
corresponding dimethylaminofluorosilanes with HI :
SiF,,(NMe),
+ 2xHI
---f
SiF,-=IS
+ xNH,Me,I
Reaction with mercuric oxide gives (SiF,),O and oligomeric fluorosiloxanes,

and with water (SiF,),O and fluorosiloxane polymers are obtained. The
pseudohalides SiF,CN and SiF,NCS are prepared from SiF,I and the corresponding Hg'I or Ag' compounds. Mercuric sulphide gives silthianes,
presumed to be (SiF,),S and (SiF,S),. SiF31reacts with NMe, to give a 1 :2
adduct, which probably has the ionic structure (SiF,,2NMe3)+I-, with
HNMe,, cleavage occurs to afford SiF,NMe,, and with ammonia, polymeric
fluorosilazanes are formed.527Very little reaction occurs between SiF, and
N20, NO, N20,, or N205 at room temperature. Below ca. -60C, SiF,
reacts with N203 to give a 1 : l adduct, probably NO+(SiF,,NO,)-, which
dissociates and decomposes above 0 "C. Both NO and N204react with Si,F,
L. M. Petrova, and A. A. Yarovoi, Metody Poluch. Khim. Reaktiv.
Prep., 1972, 31 (Chem. Abs., 1973,78, 143 262h).
523 V. P. Vasil'ev, N. I. Kokuvin, and V. N. Vasil'eva, Russ. J. Inorg. Chern., 1973, 18,
159.
524 C. E. Bamberger and C. F. Baes, J. Amer. Ceram. Soc., 1972, 55, 564.
5,s D. R. Stojakovic, S. D. Radosavljevic, and V. C. Scepanovic,J. Fluorine Chern., 1973,
3, 117.
F. Hofler and H. D. Pletka, Monatsh., 1973, 104, 1.
6,'
B. J. Aylett, I. A. Ellis, and J. R. Richmond, J.C.S. Dalton, 1973, 981.
m G. E. Revzin,
302
to produce (SiF,),O and disproportionation products. Si2CI, with NO,

N205, or N204, and SiCI, with NO usually give NOCl and polychlorosiloxanes or -silanes. SiIF, and SiH,I chiefly form disiloxanes with N20 or
NO/N2;SiH,Br and NO yield SiH2Br2and (SiH2)0,. The reaction of SiHCI,
and NOCl produces HCl , N20, and chlorosiloxanes.52s
Silicon tetrachloride and (Et,Si),O react at 260 "C in an autoclave to yield
t riet hylchlorosilane and C1,Si [OSiEt,], , which undergoes further substitution
reactions shown in Scheme 18.529The reaction of SiCI, with dichlorophos-
[( EtsSiO)zSi(NHz)2]2NH
(Et3SiO)2Si(NH2)a
/NH\
Si(OSiEt&
(Et3SiO)SSi
\
/
NH
(Et&3iO)&(NHPh),
Reagents: i, aq. NaOH, - 10 "C;ii, NH,, C,H,, 45 "C;iii, NH,,280-340 "C;iv, PhNH,, 60-65 "C
Scheme 18
phoric acid produces the compounds H [Si(P02C12),],Et20and H [Si(P02C12),].

With HSiCI,, Si(PO,Cl&, is ~ b t a i n e d . ,Xenon
~
difluoride reacts with Sic&
and SnCl, to give the metal tetrafluoride, xenon, and chlorine. A lemonyellow complex of composition 2XeF2,SnF, is formed with tin(1v) f l ~ o r i d e . 5 ~ ~
The reduction of GeCI4by silanes (Scheme 19) in the presence of an equivalent
R*R2SiHCI + GeC& + Et3N
- RlRzSiCl
R1R2SiHC1 + GeC14
- RIRz SiCI2, - HCI
Et3NHCl
+ HGeCl3
+ Et3NHCl
-HCl
HGeC13,NEts
Scheme 19
amount of triethylamine affords quantitative yields of the complex HGeCI,,NEt,. The same complex is formed if triethylamine hydrochloride is used instead of the free amine, indicating that in this case HGeCl, behaves as a
52*
529
5s0
6a1
B. J. Aylett, I. A. Ellis, and J. R. Richmond, J.C.S. Dalron, 1973, 1523.

K. A. Andrianov and N. V. Delazari, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1972,
2748.
M. Meisel and H . Grunze, 2. anorg. Chem., 1973, 400,128.
V. A. Legasov and A. S. Marinin, Russ. J , Inorg. Chem., 1972, 17, 1256.
E[ements of Group IV
303
stronger acid than HCl.532Treatment of GeCl, with bis(bromomagnesium)acetylene gives HC=CGeC3,H20.533 Intermolecular interaction in the complexes SOC12,MCl, and VOC13,MC14(M = Si or Ge) has been studied by i.r.
s p e c t r o ~ c o p y and
, ~ ~ the
~ ~ ~system
~ ~ GeC1,-TeCl, by d.t.a.536Little or no
chemical interaction is present in any case. Strong chemical interaction was
found in the PC1,-SnCl, system, in which the complex PCl,,SnCl, is formed.537
Redistribution of methyl groups and halogens takes place between Me,Pb
(n =
and SnX, (X = C1 or Br), leading to methyltin halides Me,SnX,-,
l-4).538Substitution of tin tetrachloride with the carboxylic acids RC0,H
(R = H, Me, CMe,, or CF,) or their sodium or silver salts results in the
formation of the tin dichloride dicarboxylates SnC12(02CR),. In the case of
silver trifluoroacetate, Sn(O,CCF,), is also formed. Spectroscopic datasuggest
polymeric structures with double carboxylate bridges for the formate and
acetate.539The kinetics of reduction of SnCl, by melts of tin and lead have
been studied at 300-700 OC in a continuous gas flow reactor.540Molecular
beam kinetic investigations of K, Rb, or Cs and SnCl, indicate two distinct
decay modes, one consistent with the formation of alkali-metal chloride and
the other probably the alkali-metal chlorostannite, MSnC1,.541
Methyl and phenyl isocyanides insert into the Sn-X bonds of tin tetrachloride and tetrabromide to give bis(ha1ogenocarbimino)tin dihalides :
SnX,
+ 2RNC
--).
Insertion into only one of the Sn-Cl

MeNC takes place:
Ph,SnCl,
Both Sn-Cl and Sn-C

with PhNC:542
Me,SnCl
Ph3SnBr
+ MeNC
---f
(RN=CX)2SnX2
bonds of diphenyltin dichloride by

MeN=CClSnPh,Cl
bonds of MqSnCl and Ph3PbBr undergo reaction
+ 4PhNC -+ (PhN=CMe),SnCCl=NPh
+ 4PhNC (PhN=CPh),PbCBr=NPh
+=
U.V. irradiation of a pentane solution containing SiI, and Fe(CO), results

in the formation of volatile, dark red crystals of SiI,[Fe(CO),],. A structure
N. S. Nametkin, V. K. Korolev, and 0. V. Kuzmin, Doklady Akad. Nuuk S.S.S.R.,
1972,205, 660.
533 A. A. Kuznetsov, Yu. G. Rodzolko, V. V. Kovalev, and Yu. A. Buslaev, Zhur.
neorg. Khim., 1973,18, 1416.
634 N. N. Naumova, T. S. Vvedenskaya, and B. D. Stepin, Russ. J. Phys. Chem., 1973,
47, 407.
636 N. N. Naumova, T. S. Vvedenskaya, and B. D. Stepin, Russ. J . Phys. Chem., 1973
47,264.
636 V. V. Safonov and A. V. Konov, Russ. J . Inorg. Chem., 1972, 17,233
537 M. K. Ckianova and E. S. Vorontsov, J . Gen. Chem. (U.S.S.R.),
1972, 42, 715.
538 Neth. App. 71 00,202 (Chern. Abs., 1973, 78, 4 361b).
639 A. N. Sara and K. Taugbol, J. Inorg. Nuclear Chem., 1973, 35, 1827.
640 N. F. Drobot and V. I. Evdokimov, Termodin, Kinet. Protseeov Vosstanov. Metal.
Muter. Konf., 1969, p. 127 (Chem. Abs., 1973, 79, 23 940b).
641 S. J. Riley and D. R. Herschbach, J . Chem. Phys., 1973, 58, 27.
648 A. Meller, G. Maresch, and W. Mariggele, Monutsh., 1973, 104, 557.
532
304
for this complex is proposed in which the iodine atoms function as donors to
the Fe(CO), moieties (17).543GeX (X = Br or I) reacts with R,Sn (R = Et,
Bu, or Ph) at 250 "C to form R2SnX2and R2GeX2.At 160-200 "C, the sole
germanium-containingproduct is RGeX,, whereas at 250 "C GeBr, appeared,
a yellow precipitate formed, and gases, possibly butadiene, began to be
evolved.544Heating butyl iodide with GeI, in the presence of zinc metal at
160 "C gives 85 % Bu,Ge. By similar methods, Ph4Ge, Me(CH,),GeI,,
Me(CH,),GeI,, Me(CH,),GeI,, and PhGeI, can be ~repared.54~
Tetrakis(trifluoromethy1)tin may be obtained by the reaction of S n 4 with trifiuoromethyl radicals in a radiofrequency discharge.54s
Physical Studies of Quadrivalent Silicon, Germanium, and Tin Halides.
( i ) Structural studies. X-Ray diffraction studies of bis(chloromethy1)tin
dichloride. (CICH,),SnCI,, show that the crystal is constructed of infinite
chains with weak intermolecular chlorine bridging (Sn - - - Cl = 3.71 A),
as in dimethyltin dichloride. The co-ordination at the tin atom deviates
from tetrahedral to octahedral; the ClSnCl bond angle is 97', and the CSnC
angle is 135". The Sn-C and Sn-Cl bond distances are 2.18 A and 2.37 A,
respectively (Figure 2)."'
The structure or chIoromethyltin trichloride in the gas phase has been
determined by electron diffraction. The groups are arranged about tin in a
distorted tetrahedron (LCISnCl = 105 f lo; LCSnCl = 113 f 1.5');
Sn-C and Sn-C1 bond distances are 2.23 =t= 0.01 and 2.340 f 0.005 A,
respectively. Some hindrance to free rotation about the Sn-C bond appears
to occur (Figure 3).548
Structural data for methyltrifluorosilaneand trimethylbromogermanehave
been obtained from microwave spectra. For MeSiF,, the following structural
parameters were determined: r(Si-C) = 1.812 f 0.014A; r(Si-F) =
1.574 f 0.007 A; LFSiC = 112"20' f 1" 6'. The dipole moment of the
molecule was determined to be 2.33 f 0.10 D. A barrier to internal rotation
643
544
646
546
547
G. Schmid and H. P. Kempny, Angew. Chem. Internat. Edn., 1973, 12, 670.
K. A. Kocheskov, N. V. Fomina, N. I. Sheverdina, N. N. Zemlyanskii, and V. A.
Chernoplekova, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1973, 71 1 .
N. V. Fomina, N. I. Sheverdina, E. I. Dobrova, I. V. Sosnina, and K. A. Kocheskov,
Doklady Akad. Nauk S.S.S.R., 1973, 210, 621.
R. A. Jacob and R. L. Lagow, J.C.S. Chem. Comm., 1973, 104.
N. G. Bokii, Yu. T. Struchkov, and A. K. Prokof'ev, J. Struct. Chem., 1972,13, 665.
I. A. Ronova, N. A. Sinitsyna, Yu. T. Struchkov, 0. Yu. Okhlobystin, and A. K.
Prokof'ev, J. Struct. Chern., 1972, 13, 11.
305
Figure 2 Structure of the [(C1CHJ2SnCI,1 chain in the crystal

(Reproduced from J . Struct. Ctrern., 1972, 13, 619, by permission of the
Consultants Bureau)
of 0.93 Z!Z 0.09 kcal mol-l was also deduced.549The Ge-Br and Ge-C bond
distances for Me,GeBr were found to be 2.323 f 0.001 and 1.963 f 0.006 A,
respectively, and the CGeBr angle 106.3 f 0.1.550
(ii)Infrared, Raman, and microwave data. In addition to the two microwave
studies mentioned in the previous section, the microwave spectrum of
CF3SiF, has also been measured. A value for the barrier to internal rotation
~~~
assignments have been
was deduced to be 489 f 5 0 ~ r n - l .Vibrational
C1( 2)
Cl(3)
Figure 3 Structure ofC1CH2SnCI3

(Reproduced from J . Struct. Chem., 1972, 13, 11, by permission of the
Consultants Bureau)
5p9
J. R. Durig, Y.S. Li, and C . C . Tong, J. Mol. Structure, 1972, 14, 255.
65O
Y. S. Li and J. R. Durig, Inorg. Chem., 1973, 12, 306.

D. R. Lide, D. R. Johnson, K. G . Sharp, and T. D. Coyle, J. Chem. Phys., 1972,57,
3699.
55l
306

made for methylhalogenosilanes, and torsional barrier heights determined.5528553
1.r. and Raman spectra of n-propyltin trichloride have been assigned
to gauche- and trans-isomers using normal-co-ordinate treatment. In the
liquid state both isomers are present, but only the gauche-isomer is present
in the solid.554Clark has measured the resonance Raman spectrum of Sn14?55
(iii) N.m.r. studies. Several exchange reactions have been studied by n.m.r.
techniques. The diethylamine-catalysed hydrolysis of trimethylfluorosilane in
acetonitrile solution is rapid at 38 "C, but is slowed down at low temperatures.
Orders with respect to Me,SiF, H,O, and NEt,, and approximate values of
the equilibrium constant for the hydrolysis reaction at several temperatures,
were obtained.556The exchange of electronegative groups between binary
mixtures of dimethyl- and trimethyl-tin halides has also been studied by
lH n.m.r. s p e ~ t r o s c o p y . 6 ~ ~ - ~ ~ ~
lH n.m.r. second moments of triphenyltin fluoride, chloride, and hydroxide
have been measured between 77 and 530 K for the fluoride or the melting
point for the chloride and hydroxide. In addition, spin-lattice relaxation
times have been obtained over the same temperature ranges as well as for
triphenyltin bromide.56073Gechemical shifts for GeX, (X = Cl, Br, or I)
and all twelve mixed tetrahalogenogermanes have been measured. The
shielding effect of the halogens increases in the order C1 < Br < I. The rate
of halogen redistribution between germanium atoms in liquid mixtures of
neat tetrahalogenogermanes is
(iu) Mossbauer studies. Herber has investigated the Mossbauer spectra of
diphenyltin dichloride in detail, both in the solid and in solution. In the solid,
the observed values for the isomer shift, 1.359 f 0.015 mm s-l, and the
quadrupole splitting, 2.812 f 0.015 mm sv1, partly reflect crystal-stacking
forces. In non-basic solvents, the quadrupole splitting decreases by ca.
0.20 mm s-l, and a value of 2.61 f 0.04 mm s-l is taken as characteristic of
an isolated molecule. In co-ordinating sohents, the splitting increases to
3.51 f 0.09 mm s-l as two solvent molecules co-ordinate to the metal, giving
rise to a distorted trans-octahedral complex in which the two phenyl groups
occupy axial positions.562The effects of solvents on the Mossbauer parameters of quick-frozen solutions of SnCI, and SnI, have been investigated.663
The Mossbauer spectra of the diorganotin dichlorides RPhSnCl, (R = Me,
Et, Pr, Bu, or PhCH,) and their adducts with pFidine and bipyridyl have
65a
s53
654
656
6 5
667
s69
560
661
663
J. R. Durig and C. W. Hawley, J. Chem. Phys., 1973, 58, 237.

J. R. Durig and C. W. Hawley, J. Chem. Phys., 1973, 59, 1.
H. Geissler, C. Peuker, R. Heess, and H . Kriegsman, Z . anorg. Chem., 1972,393,230.
R. J. H. Clark and P. D. Mitchell, J.C.S. Chem. Comm., 1973, 762.
~J. A. Gibson and A, F. Janzen, Canad. J. Chem., 1972, 50, 3087.
A. S. Peregudov, L. A. Fedorov, D. N. Kravtsov, and E. M. Rokhlina, J . Gen. G e m .
(U.S.S.R.), 1972, 42, 2190.
S. 0. Chan and L. W. Reeves, J. Amer. Chem. SOC.,1973, 95, 673.
S. 0. Chan and L. W. Reeves, Inorg. Chern., 1973, 12, 1704.
B. A. Dunell and S. E. Ulrich, J.C.S. Faraday I, 1973, 377.
R. G . Kidd and H . G. Spinney, J. Amer. Chem. SOC.,1973, 95, 88.
R. H. Herber, J. Inorg. Nuclear Chem., 1973, 35, 67.
A. Vertes and K. Burger, J. Inorg. Nuclear Chem., 1972, 34, 3665.
Elements of Croup IV
307
been measured.564By comparing l19Sn and 121Sbe2qQ values for isoelectronic
and isostructural compounds, the quadrupole moment of llgSn has been
deduced to be -0.062 f 0.02 x 10-28m2. The quadrupole splitting was
deduced to be negative.564a
( v ) Miscellaneous studies. The He (I) photoelectron spectra of MF, (M = C,
Si, or Ge) and MMe, (M = C, Si, Ge, Sn, or Pb) have been e ~ a m i n e d . ~ ~ ~ . ~ ~
Thermochemical data for Me,-,SnCl,
(n = 0-4)567 and for germanium
fluoride species568have been inferred from mass-spectroscopic data. Appearance potentials and translational energies of the products resulting from
several dissociative electron-capture processes for SiF, have been measured.
The heat of formation of SiF,(g) has been determined.569The dipole moments
of methylgermanium fluoride have been measured.570Polarographic behaviour of di-t-butyltin d i ~ h l o r i d e ~and
~ l triphenylgermanium halides572has
been studied. The electronic spectrum of SnCl, in the vacuum U.V. has been
rep0rted.5~~
The vapour pressures and excess free energies for the SiCl,-,hexane system have been measured.574
Complexes and Complex Anions. (i) Halide donors. A new double salt,
(NH,),SiF6,NH,NO,, crystallizes on cooling from aqueous solutions of
(NH,),SiF, and NH,N0,.576 The complexes MPbF,,GH,O (M = Co, Ni,
Zn, or Cd) and CuPbF6,4H20can be prepared from the metal fluoride or
carbonate and PbFi-. 1.r. spectroscopy indicated that the hexahydrate
complexes contain [M(H20)6]2f i0ns.5~~
An X-ray diffraction study of the
cobalt salt confirms this spectroscopic inference, the structure consisting of
discrete [Co(H20)J2+ and SiFi- octahedra joined systematically by
0 - H * Fhydrogenbondsintochains,r(Si-F) = 1.643A, LFSiF = 88.5,
9 1 .6.577A preliminary communication of another complex hexafluorosilicate,
Cu, [SC(NH,)2]lo,(SiF6)2,H20,
has also appeared, but no details concerning
the SiFi- moiety were reported.578The structure of Li2SnF,,2H20 consists of
a hexagonal close-packed array of fluorine and water molecules, with lithium
- --
564
K. L. Jaura and K. K. Verma, J. Inorg. Nuclear Chem., 1973, 35,2361.

G. M. Bancroft, K. D. Butler, and E. T. Libbey, J.C.S. Dalton, 1972, 2643.
M. B. Hall, M. F. Guest, I. H. Hillier, D. R. Lloyd, A. F. Orchard, and A. W. Potts,
J . Electronic Spectroscopy, 1972, 1,497.
A. E. Jonas, G. K. Schweitzer, F. A. Grimm, and T. A. Carlson, J. Electronic Spectro-
564.3
567
568
56D
570
571
672
573
57p
676
576
577
578
21
scopy, 1972,1,29.
T. R. Spalding, J . Organometallic Chem., 1973, 55, C65.
P. W. Harland, S. Cradock, and J. C. J. Thynne, Inorg. Nuclear Chem. Letters, 1973,
9,53.
J. L. F. Wang, J. L. Margrave, and J. L. Franklin, J. Chem. Phys., 1973, 58, 5417.
D. F. Van de Vondel and G. P. Van der Kelen, J . Organometallic Chem., 1973,55,85.
P. Leroux and M. Devaud, Bull. SOC.chim. France, 1973, 2254.
R. J. Boczkowski and R. S. Bottei, J . Organometallic Chem., 1973, 49,389.
A. A. Iverson and B. R. Russell, Spectrochim. Acta, 1973, 29A, 715.
D. V. S. Jain and 0. P. Yadav, Indian J . Chem., 1973,11,28.
L. Marosi and H. Theobald, Z . anorg. Chem., 1973, 396,185.
R. L. Davidovich, T. F. Levchishina, and T. A. Kaidalova, Zhur. neorg. Khim., 1973,
18, 621.
H. Lynton and P. Y . Siew, Canad. J . Chem., 1973, 51,227.
A. G. Gash, E. H. Griffith, W. A. Spofford, and E. A. Amma, J.C.S. Chem. Comm.
1973, 256.
308
and tin in slightly distorted octahedral interstices; four Sn-F bond distances
are 1.962 A and two are longer, 1.983 %.; LFSnF = 88.6, 91.3.679
Tetragonal distortion of the SnCli- anion occurs in 4-chloropyridinium
hexachlorostannate(rv), there being three crystallographically inequivalent
Sn-Cl bonds: 2.414, 2.419, and 2.463A. The distortion is attributed to
C1- - H-N hydrogen-bonding between cation and anion, and accounts
very well for the marked splittings in the 35Cln.q.r. signals observed for the
anion.680N.q.r. data for several other salts of SnC1;- and PbC1;- have also
been recorded.681 Thermochemical measurements on Rb2SnCl, give the
standard heat of formation as -365.5 kcal mol-l at 298 K. The enthalpy
change for the process :
--
2CI-(g)
+ SnCl,(g) -+ [SnC16]2-(g)
has been calculated to be -21.7 f 17 kcal mol-l at 298 K. SnCI, has the
same acceptor strength towards the chloride ion as TeClkm2 The X-ray
photoelectron spectra of simple and mixed hexahalogenostannates have been
measured. The tin 3d,,, binding energies of the series [SnX,,Y,]2-(X,
Y = F, CI, Br, or I) are found to correlate linearly with average ligand
electronegativities, Mossbauer isomer shifts, and estimated atomic charges
on the tin atom>83n584The vibrational spectra of the species Me3SnClr,
MqSnCl,, MeSnClT, and MeSnCli- have been reported.585The tetrahalogeno- and pentahalogeno-monophenylplumbates(w) M [PhPbX,] (M = Ph,P
or Ph,As; X = C1 or Br) and M,[PhPbX,] (M = Me,N or C,H,NX;
X = CI or Br; M = QCl,HaN2H, or Cs; X = C1) are obtained by allowing
HCl and HBr, respectively, to react with suspensions of PhPbO(0H) and
MX in ether and methanol, and also by allowing MX and products to react,
which can be obtained by the reaction of PhPbO(0H) and HCl or HBr at low
temperatures in ether. Polymeric PhPbF, can be prepared by the reaction of
PhPbO(0H) and 40 % hydrofluoric
The complex molecules TlPbCl,,
CdPbCl,, SnInCI,, and PbThCI, have been observed by mass spectrom(ii) Oxygen donors. Using complexes of SnCl, with oxygen donor ligands as
examples, Maksyutin et al. have shown that it is possible to predict n.q.r.
splittings on the basis of structural data for octahedral complexes MX4,2L,
as well as to determine the positions of the donor molecules by a simple
analysis of the spectra.588The synthesis and structures of tin(1v) halide adducts
67g
680
581
684
685
686
687
s88
E. A. Marseglia and I. D. Brown, Acta Cryst., 1973, B29, 1352.

R. C. Gearhart, T. B. Brill, W. A. Welsh, and R. H. Wood, J.C.S. Dalton, 1973,359.
T. B. Brill and W. A. Welsh, J.C.S. Dalton, 1973, 357.
M. Webster and P. H. Collins, J.C.S. Dalton, 1973, 588.
L. E. Cox and D. M. Hercules, J. Electron Spectroscopy, 1972, 1, 193.
W. E. Swartz, P. H. Watts, E. R. Lippincott, J. C. Watts, and J. E. Huheey, Inorg.
Chem., 1972,11,2632.
I. R. Beattie, F. C . Stokes, and L. E. Alexander, J.C.S.Dalton, 1973, 465.
H. Lindemann and F. Huber, Z . anorg. Chem., 1972,394, 101.
M. Binnewies and H. Schtifer, 2.anorg. Chem., 1973,395,77.
Yu. A. Maksyutin, E. N. Guryanova, E. A. Kravchenko, and G. K. Semin, J.C.S.
Chem. Comm.,1973,429.
309
of nickel(I1) and palladium(I1) dithio-oxalato-complexes [R,P], [M(S,C,O,),]
(M = Ni or Pd) have been reported. The stoicheiometries of the adducts
formed depend on the tin(1v) halide and solvent used. With SnF,, only a 1 :1
adduct could be formed, but with SnCI,, both 1 :1 and 1 :2 adducts are
formed in dichlorornethane or acetone. In acetonitrile only 1 :1 SnCl, adducts
are formed. Strong donor solvents (DMSO, DMF) cause rapid solvolysis:
[R4P12[M(SzCzOz)21
[SnX4I2 i4L
-+
[R4PI2[M(S2C02),l
+ 2SnX4,L2
Acetone solutions of the 1 :1 adducts disproportionate on standing:

2 w %[M(s2c@2)2I(snxd
3 W4pI2
[M(S,C,O,),I
+ [R,P12 [M(s2czo2),l(snx,),
The structures of the 1:1 and 1 :2 complex anions, [Ni(S,Cz0,),(SnCl,)]2and [Ni(S2Cz02)2(SnClp)2]2-,

are shown in Figure 4. In both anions the tin
atoms are octahedrally co-ordinated by four chlorine and two oxygen atoms.
In both, two Sn-Cl bond distances (mean 2.387 A) are slightly longer than
the other two (mean 2.342A). The mean Sn-0 bond distances are 2.161 and
2.212A for the 1 :1 and 1 :2 adducts, respectively.589
Tin@) chloride and bromide form 1 :1 and 1 :2 adducts with tributyl
phosphate. 1.r. and Raman studies show that the 1 :2 adducts have D4&
symmetry in dilute cyclopentaneor cyclohexane, but in concentrated solutions
or in the pure state, the bromide has C,, and the chloride C,, symmetry.
The 1 :1 complexes disproportionate in dilute solution:590
2SnX4,TBP $ SnX4,2TBP 4- SnX,
Complexes of diorganophosphinous acids, R,P(O)H, with tin(1v) chloride

have been reported.591Co-ordination of the dialkylphosphinic and dialkylphosphinothioic acids to tin in the complexes [R1R2P(0)YH],,SnX4(Y = 0
or S)is effected through the phosphoryl oxygen in both cases. The phosphinic
acid complexes lose hydrogen chloride at 120-140 'C to form the compounds
[R1R2P(0)O],SnCl,, which appear to be chain polymers of the type (18.)592
(18)
690
501
592
D. Coucouvanis, N. C. Baenziger, and S. M. Johnson, J . Amer. Chem. SOC.,1973,

95,3875.
G.Roland, B. Gilbert, J. Decerf, and G. Duyckaerts, Spectrochim. Acta, 1973,29A,
879.
A. A. Muratova, E. G. Yarkov, V. P. Plekhov, R. G. Zagetova, and A. N. Pudovik,
J. Gen. Chem. (U.S.S.R.), 1972,42,966.
A. N. Pudovik, A. A. Muratova, I. Ya. Kuramshin, E. G. Yarkova, and L. I.
Vinogradov, J . Gen. Chem. (U.S.S.R.), 1972,42,969.
310
1 :1 and/or 1;2 complexes with tin(Iv) chloride have also been prepared with
a l k o x y ~ i l a n e saromatic
,~~~
and dicarboxylic acids.5g5The dielectric
properties of carboxylic acid complexes in aromaticsolventshave been studied.
Dissociation into current-carrying ions occurs in some s y s t e r n ~N.m.r.
.~~~~~~~
data show that in solutions of SnCl, in D M F the ratio of tin atoms to co-
(a)
Cl( 1)
Figure 4 Structuresof(a)[Ni(S2C,02),( SnClg)]2-and(b)[Ni(S2C20~2(

SnCl,)]l(Reproduced by permission from J . Amer. Chem. Soc., 1973,95,3875)
ordinated DMF molecules is 4 :1 . Conductivity measurements indicate the
presence of ions, and the process:
4SnC1, 4- DMF
593
5g4
5g6
586
697
---t
SnCl,(DMF)+ 4- Sn,Cl,b
Yu. V. Kolodyazhnyi, A. S. Grischenko, K. S. Pushkareva, and 0.A. Osipov,J. Gen.

Chem. (U.S.S.R.),1972,42, 1344.
P. M. Zaitsev, Ya. A. Shuster, L. E. Semikina, A. B. Sukhomlinov, and V. S. Gudz,
J . Gen. Chem. (U.S.S.R.),
1972,42,1500.
P. M. Zaitsev, Ya. A. Shuster, L. E. Semikina, A. B. Sukhomlinov, and L. V. Udovichenko, J . Gen. Chem. (U.S.S.R.),
1972, 42, 1504.
V. N. Marchenko and A. I. Pletnev, J . Gen. Chem. (U.S.S.R.),
1973, 43,472.
V. N. Marchenko and A. I. Pletnev, J . Gen. Chem. (U.S.S.R.),1973, 43,477.
311
is s~ggested.5~~
Formation constants of complexes between methyl methacrylate and SnCI, have been measured.5ggMossbauer spectra show that the
tin(1v) sorbed from HCI and HBr solutions is present as the complex species
[SnBr4(0H),l2-, [SnBr,(0H)l2-, [SnCI5(OH)I2-,and SnC12g-.600
The structure of the Schiff-base complex bis (salicyla1dehyde)ethylenediiminodimethyltin dichloride, Me2SnCl,(salenHa, consists of polymeric
Cl(2)
C1( 1 )
(13)
Figure 4
(continued)
chains in which salenH, molecules bridge Me,SnC12 units (Figure 5). The
co-ordination at tin is almost regular octahedral, with a trans, trans, trans
arrangement of methyl groups and chlorine and oxygen atoms. The Sn-CI
bond distances (2.59, 2.64A) are very long; other tin-ligand distances are
shown in the Figure.6o1Several new Schiff-base and related complexes have
also been prepared. Adducts of MqSnCI, with several picolinaldimines
Ig8
W.G.Movius, J . Inorg. Nuclear. Chem., 1972,34,
6Dg
6oo
H. Hirai and M. Komiyama, Polymer Letters, 1972, 10, 925.

C. M. Hsu and H. S. Cheng, J. Inorg. Nuclear Chem., 1973,35,2343.
L.Randaccio, J. Organometallic Chem., 1973, 55, C58.
@O1
3571.
312
Figure 5 The structure of Me,SnCl,(salenH,)

(Reproduced by permission from J. Organometallic Chem., 1973,55, (2%)
CsH4NCH=NR (R = Me, C6H40Me-p, C,H,Me-p, or C6H,C1-p) have
been isolated, and their equilibrium constants, heats of complex formation
and thermodynamic parameters obtained.m2 The lead(1v) Schiff-base complexes (19) and (20) have also been synthesized.603The reaction of BuSnC1,
with pentane-2,4-dionein the presence of pyridine leads to the isolation of the
pyridine adduct of butyldichloro(pentane-2,4-dionato)tin(1~).6~~Some more
diaryltin dichlorideoxine complexes have been
Sams has investigated systematically the interaction of dimethyl- and diphenyl-tin dichlorides with a number of oxygen donor ligands G E O (E = C,
N, P, or S). Both 1:1 and 1:2 adducts are formed. In the solid state, the 1:2
G. E. Matsubayashi, M. Okunaka, and T. Tanaka, J . Organometallic Chem., 1973,
56,215.
N. S. Biradar, V. H. Kulkarni, and N. N. Sirmokadam, J. Iaorg. Nuclear Chem.,
1972,34, 3651.
Oo4
6os
D. W. Thompson and J. F. Lefehocz, J. Organometallic Chem., 1973,47, 103.

T. N. Srivastava, M. P. Agarwal, and K. L. Saxena, J . Inorg. Nuclear Chem., 1973,35,
306.
313
adducts all have trans methyl or phenyl groups, and except for Me2SnC1,,2CsH5N0, cis-chlorine atoms and cis donor molecules. The 1 : l adducts
appear to have trigonal-bipyramidal structures in which the organic groups
and one chlorine occupy equatorial positions, with the donor molecule and
the second chlorine atom in apical positions. Again the Me2SnC1,,CsH5N0
complex is exceptional, with both apical positions being occupied by chlorine
atoms.608Interaction of organo-tin halides with 2,2'-bipyridyl NN'-dio~ide,6~'

carbonyl-stabilized phosphorus ylides,68*6m
and diphenyl sulphoxideel0has
also been investigated. Reutov has synthesized several complexes of methyltin
606
607
608
6oo
B. V. Liengme, R. S. Randall, and J. R. Sams, Canad. J . Chem., 1972,50,3212.

V . G. Kumar Das, Inorg. Nuclear Chem. Letters, 1973, 9, 155.
J. Buckle and P. G. Harrison, J . Organometallic Chem., 1973, 49, C17.
S. Kato, T. Kato, M. Mizuta, K. Itoh, and Y. Ishii, J . Organometallic Chem., 1973,
51, 167.
610
T. N. Srivastava and K.L. Saxena, Indian J . Chem., 1973,11,294.
314
halides Me,SnX,-, (n = 0-3) and reported Mossbauer and n.q.r. data.611-613
(iii) Sulphur donors. Tin(1v) chloride forms complexes with thiols in which
the S-H bond is retained. Above room temperature, however, the complexes
are unstable, evolving hydrogen chloride.614
(iv) Nitrogen donors. Silicon(rv) fluoride forms 1:2 adducts with a wide
variety of amines and 1 :1 adducts with diamines. Solid SiF, also reacts with a
deficiency of pyridine to yield an approximately 1 :1 adduct. Dissociation of
the complexes takes place in the vapour phase, and competition experiments
indicate the order of adduct stability NH, > NH2Me > NH2P > NHMe, >
NMe,. First-order rate constants for the hydrolysis of SiF,,2NH3 and SiF,,2NH,Me are 1.0 x
and 1.9 x
s-l at 25 OC;qualitative hydrolysis
becomes more rapid in the order NH, < primary amines < secondary
amines < tertiary amines.616The adducts of SiF, and secondary aminesreadily
undergo self-defluorination on moderate heating to yield volatile aminofluorosilanes SiF3NR2 (R = Me, Et, Pr, or Bu; R2 = C,H8 or C5HIO). The
adducts of primary amines decompose less readily to afford the disilazanes,
(SiF,),NR(R = Pr, Bun, or Bus) or the silylamine SiF,NHBut. Germanium(1v) fluoride and diethylamine do not react at 130 OC?17 Condensed-phase
enthalpies of dissociation of [R,N][SiF,(NH,)] (R = Et, Pr, or C,Hll) are
in the order Et < Pr < Bu > C5H11, and a lower limit of 16.8 f 0.6 kcal
mol-1 has been suggested for the gas-phase interaction of NH, with SiFF. The
enthalpies of dissociation of the amine adducts [(C5Hl,),N] [SiF,L] (L =
MeNH,, Me,NH, or Me,N) are in the order NH3 N MeNH, < Me2NH N
Me,N?18
Electron paramagnetic resonance studies of the complex SiCl,(bipy), show
the presence of singlet and triplet forms. A spin equilibrium between the
forms (21) and (22) is thought to exist :619
CI,Si2+(bipy2-)(bipy0) ++ CI,Si(bipyo)(bipyZ-)
(21)
+ CI,Si(bipy-)(bipy-)
(22)
The complex reacts with methanol and water to give the complexes [Six,(bipy),]C12 (X = OMe or OH), which are strong 1 :2 electrolytes in aqueous
solutions. Spectroscopic investigations show them to consist of cis-octahedral
[SiX2(bipy)2]2+cations and chloride anions.620
V. S. Petrosyan, N. S. Yashina, and 0. A. Reutov, J. Organometallic Chem., 1973,
52, 315.
61z V. S. Petrosyan, N. S. Yashina, 0. A. Reutov, E. V. Bryuchova, and G. K. Semin,
J. Organometallic Chem., 1973, 5 2 , 3 2 1 .
613 V. S. Petrosyan, N. S. Yashina, S. G. Sacharov, 0. A. Reutov, V. Ya. Rochev, and
V . I. Goldanskii, J . Organometallic Chem., 1973, 5 2 , 333.
614 J. A. Douek and J. T. Spickett, J . Inorg. Nuclear Chem., 1973, 35, 51 1.
J. Mikler, Monatsh., 1973, 104, 376.
616 B. J. Aylett, 1. A. Ellis, and C. J. Porritt, J.C.S. Dalton, 1972, 1953.
617 B. J. Aylett, I. A. Ellis, and C. J. Porritt, J.C.S. Dalton, 1973, 83.
618 I. Wharf and M. Onyszchuk, Canad. J . Chem., 1 9 7 2 , 5 0 , 3450.
619 P. M. Broudy, A. D. Berry, B. B. Wayland, and A. G. MacDiarmid, J. Amer. Chem.
SOC.,1 9 7 2 , 9 4 , 7 5 7 7 .
wo D. Kumnier and H. Koster, 2. anorg. Chem., 1973, 398,279.
611
Elements of Group l V
315
The thermally unstable complexes SiCI,X,NMe, (X = H, F, Br, or I)
and their deuterium analogues have been studied at -196OC by i.r. and
Raman spectroscopy. Five-co-ordinate structures are suggested in which the
trimethylamine ligand always occupies an axial position, and X is equatorial
for H and F but axial for Br and I.621The reducedaliovalent state Snrl appears
in the Mossbauer emission spectra of SnBr4,2py and SnBr4,bipy, but only
the normal charge state is observed in the source spectra of SnC12,bipy.622
Other complexes which have been prepared are : cis-GeL,CI, and [GeL,]Cl,
(L = isonicotinic acid hydra~ide);~~,
GeCI,,L, (L = C,,H,N, C,H,,N,, or
CI2HsN2)and GeCl,,C4H,N;624tin(1v) chloride and bromide with halogenoa n i l i n e ~ , 6anisidines,626
~~
and 3-cyan0pyridine;~~~
benzimidazole complexes
of lead(1v) chloride ;s2s 1-vinylazole complexes of organotin halides ;629 and
bipyridyl and phenanthroline complexes of RPhSnCI, (R = Me, Et, Pr, Bu,
or PhCH2).630
( v ) Phosphorus donors. The 1:l adducts MX4,PMe, (M = Ge or Sn;
X = GI or Br)631and 1 :2 adducts MX4,2PMe, (M = Si, Ge, or Sn; X = C1:
M = Si; X = Br)632have been investigated by i.r. and Raman spectroscopy.
The phosphine occupies an axial position of a trigonal bipyramid in the 1 :1
adducts, whilst the 1:2 adducts were deduced to possess the trans-configuration. The trans geometry has been confirmed crystallographically for SnC14,2PEt, (Figure 6). The molecules are centrosymmetricand have bond angles at
tin within 1.3" of 90'; r(Sn-P) = 2.615 A and r(Sn-C1) = 2.445
1.r. studies show that phosphine derivatives of cyclopentadienylmanganese
tricarbonyl interact reversibly with SnC1,.634 The J(117~11gSn-31P)coupling
constant and slP chemical shift in SnC1,,2Bu3P have been measured.635
Oxygen Derivatives of Silicon, Germanium, Tin, and Lead.-The

chemistry of Group IV oxides has been reviewed.636
crystal
D. Boa1 and G . A. Ozin, Canad. J. Chem., 1973, 51,609.

J. P. Sanchez, Y. Llabador, and J. M. Friedt, J . Inorg. Nuclear Chem., 1973,35, 3557.
623 E. M. Belousova, I. N. Nazarova, and 1. I. Seifullina, Zhur. neorg. Khim., 1973,18,96.
6 2 4 S . A. A. Zaidi and K. S. Siddiqi, J . Inorg. Nuclear Chem., 1973, 35,655.
626 M. I. Usanovich, E. K. Pichugina, V. A. Glybovskaya, and 0. M. Puzyrevskaya,
1972,42,837.
6 a 6 M. I. Usanovich, E. K. Pichugina, V. A. Glybovskaya, and L. V. Vasil'yanova,
J. Gen. Chem. (U.S.S.R.),1972, 42, 834.
6 2 7 S. C. Jain, J . Inorg. Nuclear Chem., 1973, 35, 505.
6 2 8 N. Biradar and N. N. Sirmokadam, J . Inorg. Nuclear Chem., 1973, 35, 3639.
M. G. Voronkov, G. G. Skvortsova, E. S. Domina, Yu. N. Ivlev, R. G. Mirskov,
0. S. Ishchenko, and I. M. Korotaeva, J . Gen. Chem. (U.S.S.R.),
1972,42,2195.
630 IS. L. Jaura, S. K. Bhalla, B. D. Gupta, and V. K. Verma, Indian J . Chem., 1973, 11,
49.
631 D. K. Frieson and G . A. Ozin, Canad. J . Chem., 1973,51,2697.
632 D. K. Frieson and G. A. Ozin, Canad. J . Chem., 1973, 51,2685.
633 G. G. Mather, G. M. McLaughlin, and A. Pidcock, J.C.S. Dalton, 1973, 1823.
634 A. G. Ginzburg, B. V. Lokshin, V. N. Setkina, and D. N. Kursanov, J. Organometallic
Chem., 1973, 55,357.
635 A. Yamasaki and E. Fluck, Z . anorg. Chem., 1973, 396,297.
1 3 V.
~ ~I. Lebedev, Soviet Phys. Cryst., 1972, 17, 33.
621
622
316
Silicon Solid-state Chemistry. Following the pat tern set in the previous volume,
this aspect of silicon chemistry will be subdivided into four sections in which
the literature published on silicon dioxide, silicates, aluminosilicates, and
zeolites is described separately. In all four sections, emphasis will be laid on
the inorganic chemistry of these materials, and papers describing solely their
Figure 6 Structure ofSnC1,,2PEt3

(Reproduced from J.C.S. Dalton, 1973, 1823)
catalytic, adsorption, diffusion, ion-exchange, and other similar properties

will not be considered.
A comprehensive review of the chemical composition of the lunar surface,
as ascertained by analysis of samples obtained on the Surveyor and subsequent Apollo and Luna missions, has been collated by Turke~ich.~~
The lunar
surface is made up of silicate rocks, the principal minerals being calcium-rich
feldspars and pyroxenes. In many respects the chemical composition of the
maria analysed are similar to those of the terrestrial basalts. The terra regions
analysed are distinctly different from the maria in having considerably smaller
amounts of iron and titanium and larger amounts of calcium and aluminium.
Apollo missions have shown that the lunar mare material is very dry and was
produced under relatively reducing conditions.
( i ) Silicon dioxide. Theoretical calculations of the electronic structures of
the Si044
and GeOf 639 tetrahedral oxyanions have been carried out
638n63g
13~
638
6sg
A. L. Turkevich, Accounts Chem. Res., 1973, 6, 81.

J. A. Tossell, D. J. Vaughan, and K. H. Johnson, Chem. P h p . Letters, 1973,20, 329.
S. P. D o h , B. F. Shchegolev, and M. E. Dyatkina, J . Struct. Chem., 1972,13,904.
Elements of Group IY
317
using both the SCF X a scattered-wave methods38and MO calculations.s39

The results obtained from the former analysis give good agreement with the
X-ray photoelectron spectra of amorphous Si02 and fair quantitative agreement with the Si Ks, Si L2.3,and 0 K, spectra of crystalline quartz. The U.V.
spectra of fused and crystalline quartz are also reproduced extremely well by
the calculations. The valence orbitals of the SiOi- cluster were found to be
separable into three sections:
O,, non-bonding
52, 023)
non-bonding
le
It,
The participation of silicon 3d-type functions in the high-energy oxygen 2p
non-bonding orbitals was found to be very small.
An interesting investigation of the stoicheiometry of various types of
vitreous silica (quartz glass) has been undertaken by Vasserman et aZ.640*641
Several samples differing both in technology of production and in initial raw
material have been studied; the silica is always found to be oxygen-deficient,
the maximum extent of non-stoicheiometry being Si01.99942.
A correlation was
observed between the non-stoicheiometry of the silica and its electronic
properties, and it is suggested that it may be possible to study the properties
of these glasses as a function of their non-stoicheiometry.
form of crystobalite has
The crystal structure of the high-temperature (@)
been determined as a function of temperature, using a powder specimen
prepared by devitrifying pure vitreous silica at 1690 0C?42The structure has
an Si-0 distance of 1.612 f 0 . 0 0 2 ~ 4and a SiOSi angle of 146.72 f 0.41'
[cf. the corresponding structural parameters of the low-temperature (a)
form of crystobalite - 1.601 and 1.608 and 146.8', respectively]. It is thus
confirmed that the structure of p-crystobalite is disordered, resulting in an
average structure of cubic symmetry. Two separate investigations of the
morphology of quartz have been carried O U ~ ? In~ particular,
~ * ~ ~ it has been
concluded that it is best to describe the product obtained by powdering
quartz as microcrystalline
and not as an amorphous or vitreous
form of silica, as has been suggested previously.
and of / l - q u a r t ~have
~~~
The Raman spectra of a- and /l-cry~tobalite~*~
been measured. The spectra of the crystobalite samples were determined as a
840
841
642
644
645
646
I. M. Vasserman, M. P. Nikitina, and A. V. Amosov, DokZady Chem., 1972,203,193.

I. M. Vasserman, DokZady Chern., 1973, 208, 5.
A. J. Leadbetter, T. W. Smith, and A. F. Wright, Nature, Phys. Sci., 1973,244, 125.
S. White, Nature, 1973, 244, 276.
G . S. M. Moore and H. E. Rose, Nature, 1973,242, 187.
J. B. Bates, J. Chern. Phys., 1972, 57,4042.
J. Fries and R. Claus, J. Raman Spectroscopy,1973, 1, 71.
318

function of temperature (-196 to 538 "C); the spectra recorded above and
below the cc-b transition temperature (267 f 2 "C) were strikingly different
(Table 26). For example, the strong bands measured at 416 and 230 cm-l with
a-crystobalite at 25 "C were not observed in the spectra of the B-phase. The
Raman spectra of this latter phase, which exhibited only three bands, showed
that its structure should not be employed as a lattice model for non-crystalline SiO,. Energy band-structure calculations by the three-dimensional
Table 26 Bands observed in the Raman spectra of crystobalite between -196
and 538 "C (wavenumbers/cm-l)
TemperaturelT
-196
25
266
121
23 3
275
(286
110
230
275
287
95
226
416
405
426
785
(796
1076
785
795
1079
1089
278
300
538
292
275
267
776
777
777
772
1079
1077
1075
1065
28 1
1188
(1193
~'
extended Hiickel method have been presented for B-cryst ~ b a l i t e ; ~an
extended series of calculations yielding the total density of states correlates
satisfactorily with the L,,3 X-ray fluorescence spectra of silica.
A Knudsen effusion study with @-crystobaliteon a thermomicrobalance
has been carried out over the temperature range 1823-1 983 K.648Interpretation of the effusion data, based on the reactions (93) and (94), gives rise to the
standard Gibbs Free Energy of reaction (93) as AG, = 182 050 - 58.29T/K
f 2500 cal mol-l and the heat of formation of SiO(g) as H&3[SiO(g)]=
-27.9 f 3.5 kcal mol-l in the measured temperature range, and the dissociation energy as Di(Si-0) = 8.45 f 0.20 eV.
The chemistry of the functional groups present on the surfaces of silicas
continues to arouse considerable i n t e r e ~ t . B ~Several
~ - ~ ~ ~investigations based
647
648
64s
650
651
653
A. Breeze and P. G. Perkins, J.C.S. Faraday ZI, 1973, 69, 1237.

S. Nagai, K. Niwa, M. Shinmei, and T. Yokokawa, J.C.S. Faraday Z, 1973,69, 1628.
V. A. Tertykh, A. A. Chuiko, V. V. Pavlov, and V. M. Ogenko, Doklady Chem.,
1973,206,791.
B. A. Morrow and I. A. Cody, J. Phys. Chem., 1973,77,1465.
F. H. van Cauwelaert, P. A. Jacobs, and J. B. Uytterhoeven,J . Phys. Chem., 1973,77,
1470.
V. Ya. Davydov, A. V. Kiselev, V. A. Lokutsievskii, and V. I. Lygin, Russ. J. Phys.
Chem., 1973,47,460.
319
on i.r. spectroscopy have been designed to consider in some detail the nature
of the isolated -OH group present on these surface^.^^^-^^^ The adsorption of
water on silica surfaces has also been examined using i.r. technique^;^^^^^^^
the results of the studies involving the adsorption of water vapour on the
partially hydrophobic silicas, variously modified by heat treatment in the
presence of NaCl, indicate that the predominant active sites for adsorption
are the surface -OH groups, despite the presence of sodium and other
foreign elements?53In the initial stages of the adsorption the water is thought
to adsorb 'oxygen-down', forming a 1 :1 complex in which the surface -OH
groups are donors and H,O molecules are acceptors of the hydrogen bond.
At an occupation of ca. 50 % of the -OH groups the water molecules start to
aggregate into clusters. The adsorption of water on suspensions of amorphous
silica in carbon tetrachloride has been studied by i.r. spectroscopy in the
range 2500-4000 ~ m - -The
~ spectrum
. ~ ~ ~ of pure dried SiO, consisted of one
band at 3700 crn-l, which was assigned to isolated surface hydroxy-groups
interacting with the CCI, media. Although rehydration of the silica produced
bands at 3400 cm-l for the adsorbed molecular H 2 0 and at 3660 cm-l for
adjacent hydrogen-bonded surface hydroxy-groups, it did not alter the intensity of the free -OH band at 3700 cm-l even though the H 2 0 molecule is
adsorbed by hydrogen-bonding to the hydroxy-groups. A closer examination
of the problem revealed that failure to observe a decrease in the 3700 cm-l
band is not in conflict with the hydrogen-bonding concept; indeed, it is
difficult to visualize a hydrogen-bonded configuration which does not leave
at least one free -OH bond. For example, on sparsely hydroxylated surfaces,
configurations (23) and (24) may occur in which there are two free -OH
groups for each silanol-H,O pair [configuration (24) corresponds to the
H
\ /
I
..o,
H' '
663
6154
H.. H,
''9
K. Klier, J. H. Shen, and A. C.Zettlehoyer, J. Phys. Chem., 1973, 77, 1458.

W. D. Bascom, J . Phys. Chem., 1972,76, 3188.
320

'oxygen-down' complex of ref. 6531. If the silanols are close enough ( < 6 A)
to permit water to bridge between them, configurations (25) and (26), in
which the ratio of free -OH group to silanol would be 1 :1, may be formed.654
The chemisorption of ammonia on silicas has been studied using i.r.
spectroscopic techniques by two groups of a ~ t h o r s ~
in ~an~ attempt
n ~ ~ ~ to
resolve the mode of ammonia adsorption and to determine the role of chlorine
impurities present in the silica in the adsorption process. Blomfield and
Little655concluded that dehydroxylated silicas contain sites which dissociate
NH, to form Si-NH2 groups. The presence of chlorine in the silicas was
found not to be a prerequisite for the chemisorption process. It was also
observed that although the adsorption of water can still take place in the
presence of amino-groups on the silica surface, the chemisorption of ammonia
as Si-NH2 groups is blocked by pre-adsorption of water vapour. It was thus
concluded that it is possible that both water and ammonia react with the same
type of sites of dehydroxylated silicas but water can also react with sites
which are not involved in the chemisorption of ammonia. The fundamental
i.r.-active bands attributable to surface amino-groups observed in this
investigation655are compared to those found by Hert1656in Table 27.
Table 27 Observed i.r. frequencies attributable to Si-NH,

groups (wavenumbers/cm-l)
Vsym
Vanti sym
ref. 655
ref. 656
3450
3444
3 540
3 540
1550
1555
The samples were prepared in the latter study by treatment of a preheated

(800 "C)silica with CCI, vapour at 420 "Cfor 15 minutes followed by evacuation and addition of ammonia. When various gases were added to the system
at room temperature, the above tabulated frequencies were perturbed owing
to hydrogen-bonding interactions. The observed frequency shifts were
compared to those of the corresponding mode of the surface -OH group
observed under identical conditions. The relationship between the two shifts
(examples are collated in Table 28) is approximately linear although there is
scatter in the points; the amine band shifts are approximately 20% as great
as the hydroxyl band shifts.
A similar i.r. study of the interaction of secondary and tertiary amides with
the surface of a silica has been carried o ~ t .It ~has~been
~ shown
* ~ that
~ ~the
free -OH group of the surface interacts with the carbonyl group of the amide
function, and the NH group of the secondary amide is not bound to the
s u r f a ~ e . 6The
~ ~ observed frequency shifts show that the hydrogen-bonds to
665
G. A. Blomfield and L. H. Little, Canad.J. Chem.,1973, 51, 1771.

Hertl, J. Phys. Chem.,1973, 77,1473.
J. Nechtstein, Bull. SOC.chim.France,1973, 913.
J. Nechtstein and B. Sillion, Bull. SOC.chim. France,1973, 917.
lli6 W.
657
66*
321
Table 28 Hydrogen-bonded frequency sh$ts on silica surfaces

AvNH(3444)lcm-1 AvoB( 3 747)lcm-I
Adsorbate
Carbon tetrachloride
n-Pentane
n-Hexane
Carbon disulphide
Trichloroethylene
Bromobenzene
Nitrobenzene
Methyl iodide
Acetaldehyde
Diethyl ether
Trimethylamine
7
8
11
14
18
24
25
28
46
89
198
45
45
30
60
60
95
112
125
280
460
975
the surface are stronger than the intermolecular hydrogen-bonds on the

amides. The influence of R1 and R2 substituents of the secondary amides
R1CONHR2on the hydrogen-bonds between the 2 0 function of the amide
and the -OH of the silica has also been considered.g58
The reactions of halogen-containing molecules with silica surfaces have
been studied using various physicochemical
A combination
of i.r.-spectroscopic kinetic data and chemical analysis has been used to
interpret the reactions of a number of chlorinated compounds (PCI,, BCI,,
CCI,, CI,, TiCI,, SnCI,, GeCI,, and COCI,) with the surface of silica.659
As well as reacting in a manner analogous to that in which SiC14reacts, viz.
+ SiClp +\--Si--O-SiCls
\Si-OH
/
<
+ HCl
the metal chlorides also give rise to a concurrent direct chlorination of the
surface hydroxy-groups:
An attempt has been made, on the basis of gravimetric and spectroscopic

investigations of the kinetics of chemisorption of Me,SiCl on silicas of differing degrees of hydration, to explain the chemistry involved in the modification
of the surface structure according to the equation?O
\
-Si-OE
/
MesSiCl + ?&--O--SiMq
HCI
The effect that the degree of hydroxylation of a silica surface has on the
chemisorption of VOCI, on that surface has also been examinedg61The
659
660
661
M. L. Hair and W. Hertl, J . Phys. Chem., 1973, 77,2070.

V. A. Tertykh, A. A. Chuiko, V. M. Mashchenko, and V. V. Pavlov, Russ. J. Phys.
Chem., 1973,47, 85.
S.1. Koltsov, A. A. Malygin, A. N. Volkova, and V. B. Aleskovskii, R u m J . Phys.
Chem., 1973,47,558.
322
Inosganic Chemistry of the Main-group Elements

mechanism of the chemisorption interaction has been found to depend on the
concentration of -OH groups on the silica surfxe. Thus at an -OH content
of 3.23 mmol g-l, VOC1, reacts with three hydroxy-groups to form (27).
7-OH
7"-O\
-Si-0
At lower -OH concentrations (2.66-1.93 mmol g-l), reaction takes place

with either 3 or 2 hydroxy-groups to give (27) or (28) respectively, and a
further decrease in -OH content to 1.17 mmol g-l results in interaction with
either two or one hydroxy-groups with the formation of (28) or (29), re-
spectively. The V-C1 bonds in the latter products are susceptible to hydrolysis, and as a consequence the total number of hydroxy-groupsin the specimen
may be increased beyond a concentration of one hydroxy-group per surface
silicon
The mechanism of the reaction of silica with phosphoric acid in aqueous
solutions has been examined.662The reactant acid molecules are readily sorbed
by the surface of the silica, thereby forming donor-acceptor complexes (30)
H
B. M. Mitsyuk, Rum. J. Iizorg. Chem., 1972, 17, 471.
323
with hydrated silicon atoms, thus retarding the dissolution of the silica in the
phosphoric acid. However, the introduction of H+ cations into the solution
(addition of strong acid) alters the mechanism of the interaction. The protons
enter into donor-acceptor bonding with the donating oxygen atoms of the
surface hydroxy-groups, thus facilitating attack by the phosphoryl oxygen of
the phosphoric acid molecule on the neighbouring silicon atom; the protonated hydrogen atom of the acid also reacts with the siloxane oxygen with the
formation of the complex (31). This complex readily breaks at the Si-0-Si
linkage to yield a molecule containing Si-0-P
bonds, as shown.
\
\/
-Si--.O-Sj-O.
.
/ H.
\8
0--P
HO
/H
.
H
\
-Si-OH
/
(H0)20P-O--Si-OH
HC
O
H
(3 1)
A quantitative determination of the concentration of hydroxy-groups on

silica surfaces using dimethylzincbis(tetrahydrofuran) as reactant has been
described.663Methane, produced according to reaction (95), is quantitatively
analysed, one mole of methane corresponding to a single -OH group.
-.%-OH
\
bi-0
Zn(CH&,2CaHsO
\ Zn + 2CH4 + 2C4H80
(95)
7si-oH
A considerable number of papers describing the results of experiments
carried out using mixed oxides, one component of which is silica, have been
published. The majority of these communications, however, describe the
catalytic activity of these materials and hence are outside the scope of this
Report; those included describe some aspect of the inorganic chemistry of the
mixed oxide systems.
The modification of silica by boron oxide has been studied by measuring
the extent of impregnation of B,O, in the silica as a function of both time
and temperature.664A condensation mechanism is proposed for the impregnation on the basis of the structural variation of the modified samples. The
reactivity of surface hydroxy-groups present on B,O3-SiO2 samples has been
compared with that of hydroxy-groups present on pure silica surfaces from
an analysis of the results of simple coupling reactions.665Several pertinent
663
665
22
W. Hawke, Z . anorg. Clzem., 1973, 395, 191.

W. Heyer and F. Wolf, Z . anorg. Chem., 1972, 393, 50.
M. L. Hair and W. Hertl, J . Phys. Chem., 1973, 77, 1965.
324
observations were noted:

(a) The presence of boron on the surface enhances the reactivity of the surface
Si-OH groups.
(b) The B-OH group is more reactive than the Si-OH group.
(c) For the coupling agents studied [Me,SiCl, Me,SiCl,, (Me,Si),NH] the
surface bond formed is fairly stable to 400 OC in uacuo.
( d) The surface bonds formed from Si-OH groups are partially hydrolysable
with H 2 0 vapour at 400 'C, whereas those formed from B-OH groups are
totally hydrolysable.
(e) The B-OH groups on the surface are present in both single and geminal
configurations.
(f)The presence of boron on the surface causes a larger decrease in the
extinction coefficient of the Si-OH band with increasing temperature than
occurs on pure silica.
The surface chemical properties of the analogous A1,03-Si02 oxide system

have been investigated by a number of physicochemical m e t h 0 d s . 6 ~ ~From
8~~~
an analysis of the results of adsorption, exchange, i.r. and e.s.r. spectroscopy,
and chemical analysis, it has been established666that there are strongly acid
Bronsted centres, less acidic Lewis and Bronsted centres, and very weakly
acidic -OH groups present on these surfaces. When added from non-aqueous
solution with increasing concentration, alkali was found to contaminate
Bronsted centres preferentially, thereafter Lewis and Bronsted centres
simultaneously, but only at high alkali concentrations were the very weakly
acidic surface -OH groups contaminated. The electron-donor properties of
the Al2O3-Si0, and Ti0,-Si02 system surfaces have been estimated using
TCNQ adsorption techniques.667When TCNQ was adsorbed onto these surfaces from an acetonitrile solution, the oxide surfaces acquired a coloration
(caused by the formation of TCNQ anion radicals on metal oxide surfaces)
characteristic of each oxide. Both mixed oxide systems showed lower radicalanion-forming ability (i.e. electron-donating power) than the parent oxides
Si02, A1,0,, and Ti02.
The nature of the oxygen species adsorbed on Ce02-Si0, supported catalysts has been investigated by e.s.r. techniques using oxygen enriched with
1702?* The e.s.r. spectra are consistent with the adsorption of oxygen as OF
at 77 K ; the 0~is thought to be adsorbed with the internuclear axis along the
surface of the catalyst at a site corresponding to a cerium ion. There is some
evidence that interaction with the metal-ion orbital perturbs the energy levels
of the adsorbed 0, ion.
(ii) Silicates. A vast number of investigations of the structures of silicates
have been undertaken. Whereas the majority of these define the precise
866
667
66s
H. Bremer, K.-H. Steinberg and T.-K. Chuong, 2.anorg. Chem., 1973, 400, 115.
H. Hosaka, N. Kawashima, and K. Meguro, Bull. Chem. SOC.Japan, 1972,45,3371.
M. Che, J. F. J. Kibblewhite, A. J. Tench, M. Dufaux, and C. Naccache, J.C.S.
Faraday IZ, 1973, 69, 857.
325
geometry of the silicate structure, a smaller
describe the general
morphology of the two- and three-dimensionallattice framework. The former
will be discussed in order of increasing complexity of the silicate structure
(i.e. decreasing Si:O ratio); the latter will not be considered in detail.
A review of those silicates containing octahedral SO, groups has been
effected, and a total of 37 references are q ~ o t e d . A
6 ~review
~
of the hydrothermal method for the synthesis of crystals has been compiled by Kuznetsov
and lob ache^;,^^ included in the review is a detailed consideration of the
growth of silicates, aluminosilicates, and other related minerals.
The application of the formation of trimethylsilyl derivatives to the study
of silicate structures has been discussed with particular reference to the sodium
silicate hydrates Na,H2Si04,nHz0 (n = 4, 5 , and 8) and the mineral hemimorphite, Zn,(OH)2Si20,,Hz0.67*The technique is based on the extraction
of silicate ions from crystalline and amorphous solids as their stable trimethylsilyl derivatives followed by separation by g.1.c. Although it was
found necessary to control the conditions of the trimethylsilylation reaction
very carefully, it was concluded that the method is universally applicable to
all silicate structures, including those soluble in water.
The newly prepared alkali-metal silicate Li,SiO, has been shown to be
isostructural with L ~ , C O ~ ~itOis, hexagonal,
;~~~
space group P6,C,, with cell
parameters a = 5.42, c = 10.63 A.
Structural investigations of both Na3HSi0,,676by X-ray methods, and
NaH3Si0,,677by n.m.r. techniques, have been undertaken. The crystal structure of Na,HSiO, was found to be orthorhombic, space group Pbca, with
unit-cell parameters a = 11.78, b = 10.94, c = 12.96A?76The co-ordinates
of all the atoms, including the hydrogen atoms, were refined by the method of
least squares to an R value of 0.05. It was concluded that the silicon-oxygen
tetrahedra are linked by pairs of hydrogen bonds to form groups with composition Siz0,(OH)2 (32). Extremely high strength must be assigned to this
hydrogen bond, the distance between the oxygen atoms which it joins being
2.560 f 0.003 A, which is considerably less than the length of the edges of the
(32)
670
671
672
673
674
675
676
D. A. Jefferson and M. G. Bonn, Nature, Phys. Sci., 1973,245,43.

B. B. Zvyagin, S. V. Soboleva, Z . V. Vrublevskaya, A. P. Zhukhlister, and A. F.
Fedotov, Soviet Phys. Cryst., 1972, 17,466.
V. A. Shitov and B. B. Zvyagin, Soviet Phys. Cryst., 1973, 17, 1024.
J. Bensted, S . Varma, and S. Prakash, Klei. Keram., 1973, 23, 66.
V. A. Kuznetsov and A. N. Lobachev, Soviet Phys. Cryst., 1973, 17, 775.
S. K. Sharma, L. S. Dentglasser, and C. R. Masson, J.C.S. Dalton, 1973, 1324.
W. Schartau and R. Hoppe, Naturwiss., 1973, 60,256.
Yu. I. Smolin, Yu. F. Shepelev, and I. K. Butikova, Soviet Phys. Cryst., 1973,18,173.
C. Dorkmieux-Morin and E. Freund, Bull. SOC.chirn. France, 1973,418.
326

SiO, tetrahedron. The l H n.m.r. spectrum observed for NaH,SiO, is consistent
with the theoretical formula Na3SiO(OH),.677
The detailed structure of forsterite, Mg2Si04, an olivine-type material,
has been studied by both vibration-rotati~n~~~
and e.p.r. spectro~copy.6~~
The i.r. and Raman spectra of various isotopically substituted species of
forsterite have been measured;678new assignments of the bands have been
obtained from a group-theoretical analysis of the olivine structure and the
24Mg-26Mg and 28Si-30Si isotopic shifts. The e.p.r. spectrum of low concentrations of Fe3+cations in synthetic forsterite has been observed at 9 GHz
and 35 G H Z . ~It
' ~is concluded from the results that the Fe3+ cations are
ordered in the octahedral M(2) sites of the olivine-type structure; neither the
valence state nor the site occupancy of the Fe3+ cations is altered by heat
treatment up to 110 "C.
The distribution of the cations in olivine, (Mg, Fe),SiO,, has been determined from single-crystal Mossbauer studies.680The variation of the ratio of
peak areas of the quadrupole-split lines of the high-spin Fe2+(d6)cation as a
function of crystal orientation has allowed the Fe2+cation occupancy of the
octahedral M(1) and M(2)sites to be identified; the results indicate that there
is an even distribution of the Fe2+cations between these sites. This result is in
conflict with recent X-ray studies of natural olivines, which did not show any
cation ordering in the octahedral sites.680
An X-ray powder diffraction investigation of the compound Ba,Zr,Si301,,681
prepared by heating a stoicheiometric mixture of BaCO,, ZrO,, and SiOz
to 1450 "C [reaction (96)], has shown it to be isostructural withK,Mg,(SO,),;
2BaC0,
+ 2Zr0, + 3Si0,
Ba,Zr2Si30,,
+ 2C0,
(96)
it is cubic, of space group P2,3, with cell parameter a = 10.299 A.

The crystal structures of the synthetic materials Ce4.,,[SiO4],O and
Dy,.,,[GeO,],O
have been shown to be analogous to that of apatite,
Ca5(P04),F.682The lattice constants of these compounds are compared with
those of apatite and other analogous compounds in Table 29. Crystals of a
Table 29 Lattice parameterslA of apatite-type materials
Apatite
a 9.34
c 6.88
D)'4.67(GeO,&O
9.200
6.808
Cea.a7(Si04)30 L%tm(Si04)30 Sm4.&3O4)3O

9.736
7.1 16
9.55
7.14
9.33
6.89
new lanthanide silicate Yb,(SiO,),CI have been prepared by vapour-transport

methods in a chlorine atmosphere.6s3 A complete single-crystal structural
M. Th. Paques-Ledent and P. Tarte, Spectrochim. Actu, 1973,29A, 1007.
A. Chatelain and C. A. Weeks, J . Chem. Phys., 1973, 58, 3722.
J, F. Duncan and J. H. Johnston, Austral. J . Chem., 1973, 26, 231.
R. Masse and A. Durif, Compt. rend., 1973, 276, C, 1029.
w2 E. L. Belokoneva, T. L. Petrova, M. A. Simonov, and N. V. Belov, Souiet Phys.
Cryst., 1972, 17,429.
683 C. Ayasse and H. A. Eick, Inorg. Chem., 1973, 12, 1140.
679
327
analysis showed that the crystal is orthorhombic, a = 6.731, b = 17.556,
c = 6.129 A, with four formula units in space group Pnrna. The Yb atoms are
in two sites and are eight-co-ordinated as YbO,CI, square antiprisms and as
Yb0,Cl dodecohedra that can also be described as Yb(SiO,),Cl octahedra.
The complex silicophosphates Sr2Ln,(Si04),(P0,)0 (Ln = La, Nd, Y , or Er)
have been prepared;684crystal optical studies, X-ray diffraction, and i.r.
spectroscopy have shown that the compounds have the apatite structure.
Various physicochemical properties of these compounds have been examined
and their unit-cell parameters calculated.
A general review and discussion of the crystallochemical features of mixed
anion frameworks has been collated by a group of Russian authors;685in
particular, the properties of the pyrosilicates Na,ZrSi,O7 and Na,ScSi,O,
were considered. The i.r. and Raman spectra of the pyrosilicates and pyrogermanates M,Pb,Si,O, and M,Pb,Ge,O, (M = K, Rb, or Cs) have been
investigated and compared with the spectra deduced from group-theoretical
analyses.ss6 The experimental results are fully consistent with a true D,,
symmetry of the pyrosilicate or pyrogermanate group (i.e. with a linear
bridge configuration).
The new alkali-metal pyrosilicates M,Si,O, (M = K, Rb, or Cs) have been
prepared and been shown to be isostructural with KGCo,O,, K6Ge20,, and
K,Ti,O, ;687 their monoclinic unit-cell parameters are summarized in Table 30.
Table 30 Lattice parameters of alkali-metal and scandium pyrosilicates
Compound
&Si&
Rb&O,
Cs6Si,0,
SczSiz07
a/A
b/A
CIA
6.45
6.75
7.14
6.503
8.88
9.20
9.53
8.498
11.13
11.52
12.03
4.687
B
126.8"
126.9"
126.6"
102'46'
As might be expected, the size of the unit cell increases with increasing cation
size. The crystal structure of thortveitite, Sc,Si,O,, has been refined;688the
unit-cell parameters of the monoclinic crystal are also collated in Table 30.
Thermal treatment of the monoclinic (/I-)
phase of thulium pyrosilicate
under high pressure has given rise to a high-temperature monoclinic ( y - )
form of Tm,Si,O, and a new form X, unknown in the pyrosilicate series.68g
The region of formation under pressure of the forms y , X, and the previously
known triclinic (a-) form as well as the crystallographic parameters of aand y-forms have been determined by powder diffraction analysis (Table 31).
684
685
u8u
687
688
688
N. F. Fedorov, I. F. Andreev, and Sh. Yu. Azimov, Russ. J. Inorg. Chern., 1972, 17,
1537.
A. A. Voronkov, R. G. Sizova, V. V. Ilykhin, and N. V. Belov, Soviet Phys. Cryst.,
1973, 18,67.
P. Tarte, M. J. Pottier, and A. M. ProcBs, Spectrochim. A d a , 1973, 29A, 1017.
W. Schartau and R. Hoppe, Naturwiss., 1973, 60, 256.
Yu. I. Smolin, Yu. F. Shepelev, and A. P. Titov, Soviet Phys. Cryst., 1973, 17, 749.
C. Bocquillon, C. Loriers-Susse, M. Dellalian, and J. Loriers, Compt. rend., 1973,
276, C . 543.
328
Table 31 Lattice parameters of thulium pyrosilicate
Compound a/A
cc-Tm2Siz07 6.62
y-TmzSiz07 5.54
b/A
CIA
uI0
PI"
yI"
6.57
10.77
12.02
4.68
94.4
92.5
96.1
91.4
The transformations B 4 cc and 4 y are accompanied by an increase in

density of 9% and 2 % respectively. At normal pressure the a- and Xmodifications of Tm2Si20, are stable up to 900 O C , above which they transform into the P-form.
Several investigations of the chemistry of stoicheiometricallysimple 'metasilicates' have been undertaken.sgMgsThe l H n.m.r. spectra of Na2Si0,,5H,0
and NaSi0,,9H20 were measured in an attempt to define their theoretical
formulae.gg0The formulae Na2[SiO,(OH),] ,4H20and Na, [SiO,(OH),] ,8H20
could not be confirmed within the framework of the spectroscopic analysis
employed (i.e. by resolution of the spectrum into a peak characteristic of H 2 0
and another of -OH). By considering H,O+ as an intermediary, it was
possible to obtain an acceptable representation of the nonahydrate, as
Na2(H,O),SiO3,6H2O, but not of the pentahydrate. Species of hydrated
lithium metasilicate, Li,SiO,,nH,O (n = 0.09-1.25) have been prepared
from mixtures of aqueous solutions of lithium hydroxide and sodium silicate
at 25-270 0C.691%Ray diffraction studies show them to be isostructural
and analogous to the orthorhombic metasilicate Li2Si03. Several physicochemical properties of the compounds have been investigated as a function
of water content.
An experimentalsg2and theoreticalss3 analysis of the properties of alkalimetal and alkaline-earth-metal silicates and germanates M2Si03and M2Ge0,
(M = Li, Nayor K) and MSi0, and MGeO, (M = Mg, Ca, or Ba) has been
carried out. The behaviour of the two types of cations in silicate and germanate systems has been found to be different;s92depending on the type of
cation, the variation of characteristic physicochemical parameters (e.g.
melting point, stretching and deformation vibration frequencies of the
MO: tetrahedra, and the effective charge on the oxygen ions) is more
pronounced for germanates than for silicates. The theoretical analysissg3
has shown that the state of the Op,--Si (or Ge)d, donor-acceptor interactions determines, together with other factors, the properties of silicates
and germanates such as melting point and capacity for glass formation.g93
For example, with increasing effectiveness of the w-bonds there is an increase
in the rigidity of the Si-0-Si
(Ge-0-Ge)
bond angles which effectively
reduces the capacity of the compound for glass formation.
6go
6g1
693
6*4
696
C. Dorkmieux-Morin and E. Freund, Bull. SOC.chim. France, 1973,418.

F. F. Barkova, V. N. Kolysheva, I. A. Poroshina, M. I. Tatarintseva, and A. S.
Berger, Russ. J. Inorg. Chem., 1972,17, 1519.
V. V. Tarasov and P. A. Soboleva, Rum. J . Phys. Chem., 1972, 46, 529.
V. V. Tarasov and P. A. Soboleva, R u m J . Phys. Chem., 1972,46,605.
J . M. Gaite and J. Michoulier, J. Chem. Phys., 1973, 59,488.
M. S. Bilton, T. R. Gilson, and M. Webster, Spectrochim. Acta, 1972, 28A, 2113.
R. Masse and A. Durif, Compt. rend., 1973,276, C , 1029.
329
A study of the e.p.r. spectrum of the Fe3+cation in diopside CaMg(Si0,)s
and spodumene LiAl(SiO,), has been made;694it has been deduced from the
results that the Few cation is situated in the octahedral M(1) sites. It has also
been shown that the M(1) site is smaller and more distorted in spodumene
than in diopside and that there is a large tetragonal distortion along the
M1-Oll direction. The vibrational spectra of the pyroxene minerals enstatite
(Mg, Fe),Si206 and augite (Ca, Mg, Fe)$i@g are reported, and assignments
are discussedon the basis of the known chain-type structures of the minerals.gg5
The metasilicate BaZrSisODhas been prepared at 1000 "C according to the
reaction :sgs
BaCOI
ZrOP + 3Si02 -+ BaZrSi,O, + CO,
The X-ray powder diffraction data obtained from this material show it to be
isostructural with bentonite BaTiSi,O,; it is hexagonal, space group P6C2,
with unit-cell parameters a = 6.755 f 0.004A, c = 9.980 f 0.010 A.
The crystal structures of four somewhat more complex silicates based on
(SO3), units have been e l u ~ i d a t e d . ~ Scawtite,
~ ~ - ~ ~ the calcium silicate
Ca,(Si6O18)C03,2H2O, contains two formula units in the monoclinic cell ;e97
structure refinement in space group I2lm was satisfactory for most of the
structure but problems with the carbonate groups require either disorder in
this space group or an ordered pattern in a lower space group, perhaps Im.
The structure consists of layers of octahedrally co-ordinated calcium atoms
alternating with layers of Si,OI8 rings and CO, triangles. The water molecules
belong to the calcium octahedra. The geometry of the Si6OI8ring is shown in
Figure 7 .
The crystal structures of specimens of verplanckite,Sg8nenadkevichite,sgD
and e ~ d i a l y t e 'have
~ ~ also been determined. Verplan~kite,6~*
(Mn, Ti, Fe)6(OH, O)2(Si4012)3Ba,2Cl,g(OH,H20),,
is a barium chloride silicate with an
open framework; its structure has been recognised as an example of a new
kind of coinpound which consists of a wide-open framework, wholly or
partly silicate, filled by Ba and C1 atoms and OH or H20 groups. The voids
in verplanckite (free diameter 7.2 A) approach the dimensions of the openings
found in the most open zeolites. The structure of nenadkevichitesgg(Na,
K)(Nb, Ti)(O, OH)Si20,,2H,0 consists of square rings of silica tetrahedra
Si4OI2joined together by chains of NbO, octahedra. Large cavities in the
structure accommodate Na and K in two partially occupied sites and H 2 0 in
two fully occupied sites; hydrogen-bonding between the two water molecules
is indicated by the bond length (2.979A). The specimen examined had a
relatively high Nb:Ti ratio of 2.76: 1.18; other minerals in the series contain
progressively more Ti until the mineral labuntsovite, essentially (Na, K, Ba)
Ti(0, OH)Si206,1.5H20,
is attained. The crystal parameters of the three
w7
69B
'0
J. J. Pluth and J. V. Smith, Acta Cryst., 1973,B29, 73.

A. R. Kampf, A. A. Khan, and W. H. Baur, Acta Cryst., 1973,B29,2019.
G. Perrault, C. Boucher, J. Vicat, E. Cannillo, and G. Rossi,Act0 Cryst., 1973,B29,
1432.
V. M.Golyshev, V. I. Simonov, and N. V. Belov, Soviet Ph.8. Cryst., 1973, 17,993.
330

O ( 4 ) nr31
O(5)
n[tl Q(4I
Figure 7 Geometry of the Si6013ring

minerals scawtite, verplanckite, and nenadkevichite are summarized in

Table 32. The framework of a specimen of e~dialyte,~OO
a complex silicate of
Zr, Fe, Ca, and Na, has been found to have the composition Na12Ca6Fe3Zr3
(Si30,)2[Si9024(OH)3]2;
this configuration is similar to that found in previous
structural investigations of eudialyte samples.
Table 32 Crystal parameters for s ~ a w t i t e , 6 ~

verplanckite,Bga
~
and nenadkeuichiteesS
Symmetry
Space Gp.
alA
b/A
CIA
Scawtite
Verplanckite
Nenadkevichite
Monoclinic
Hexagonal
Orthorhornbic
12/m
P6/mmn
Pbam
10.118
16.398
15.187
7.408 14.198
6.626 lOO"40'
7.200
7.148
-
Howieite,'Ol Na(Fel', Mn, Mg, Fe'", AI)12Si120,(OH),o,has been shown

to possess a new silicate structure intermediate between chain and sheet
silicates; it is also suggested that other related rock-forming minerals such as
stilpnomelane may have similar structures. The unit cell of howieite is triclinic, space group P1 or Pi,with parameters a = 10.170(4), b = 9.774(4),
c = 9.589(4)A; a = 91.22(5)", = 70.76(5)", y = 108.09(5)'. It is a chain
silicate with garland 8-shaped chains somewhat hybrid between single and
double chains (33). These silicate chains are attached with their corners to a
band formed by four rows of iron octahedra, which are the prominent feature
of the structure.
'01
H.-R. Wenk, Naturwiss., 1973, 60,254.
331
The crystal structures of the formally analogous silicates Na2Mg2Si6015702

and [Cu(NH2CH2CH2NH2)2],,Sis020,38H20703
have been described in detail.
The earlier claim that the anion of Na2Mg2Si,01, was a new type of silicate
anion704when first described has been retracted by the authors, Cradwick
and Taylor;702since publication it has come to their notice that this material
is isostructural with tuhualite, (Na, K)2Fe~rFe~1rSi,20,0,H20,
first reported
by Merlino705in 1969. The anions in these silicates are corrugated ribbons two
tetrahedra wide and are made up from rings of four tetrahedra fused together. In the case of Na2Mg2Si,01,, some of the Mg2+cations are tetrahedrally co-ordinated and the structure could alternatively be described as being
based on a framework with some of the tetrahedral sites occupied by Mg2f
and a 7/15 ratio of tetrahedral cations to oxygen. The remaining Mg2+cations
are octahedrally co-ordinated and, of the Na+ ions, some have 9 and others 10
oxygen neighbours within 3.1 A. The three-dimensional crystal structure of
[CU(NH~CH~CH~NH~)~]~,S~,O~,,,~~H~O~~~
has been shown to be triclinic,
with unit-cell parameters a = 10.77, b = 15.62, c = 13.89 A; cc = 106' 62',
= 110' 18', y = 72' 5', in the space group Pi. The silicate anion Sis08has been shown to consist of two rings each with four Si and four 0 atoms
linked to form a cage (34). The anion and the Cu(NH2CH2CH2NH,),cations
Si-0-Si
' 0
'04
M. E. Cradwick and H. F. W. Taylor, Acta Cryst., 1972,B28, 3583.

Yu.1. Smolin, Yu. F. Shepelev, and I. K. Butikova, SooietPhys. Cryst., 1972,17,10.
M. A. Cradwick, K. A. Shahid, and H. F. W. Taylor, Nafure,Phys. Sci.,1972,236,
'OS
110.
S. Merlino, Science, 1969, 166, 1399.
703
70s
332
Table 33 Unit-cellformulae of montniorillonites
Sample
Layer silicate
Unit-cellformula
1 Hectorite
CU0.21[Mg5.4~Li0.68A10.021Si~."00~o(F,OH)a
2
Montmorillonite (a) C U o ~ ~ ~ ~ ~ ~ . ~ ~ ~ ~ o . 3 ~ ~ g o .
3
Montmorillonite (b) ~ ~ 0 . ~ ~ ~ ~ ~ ~ . ~ ~ ~ ~ 0 . 3 ~ ~ g 0 . B 5 1 ~ ~ ~ o . 2 2
4
Montmorillonite (c) Cuo. 63[A] .,&, . lMgl .201 @lo .,,3i7 . W ) O ~ ~ ( O H ) ~
5
Saponite
CUO.
6 I [Mgj. ~ 2 ~ ~ 0 . ~ ~ ~ ~ 0 . 0 4 ~ ~ 0 . 0 s l
6
Vermiculite (a)
C U i . 0 o [A16.,oFeo.
oeMgs .06] (A12.,,Si5.72)020(0H)4
7 Vermiculite (b)
CUO. Y S [Al,.iaFei.osMg4.ssI(Alz . I ~ S ~ ~ . B Q ) Q ~ Q ( O H ) ~
are joined together by a system of hydrogen bonds involving water molecules;
there are also direct hydrogen bonds between cation and anion.
The results of two fascinating e.s.r. investigations of copper(I1) cations on
the interlamellar surfaces of expanding layer-lattice silicates (known as
montmorillonites or smectites) have been r e p ~ r t e d .The
~ ~ stereochemistry
~.~~~
of hydrated copper(@ ions on the surfaces of samples of hectorite, montmorillonite, saponite, and vermiculite (Table 33) has been studied by observing the anisotropic components of theg factor in the e.s.r. spectra of oriented
film samples at room temperature.706When a monolayer of water occupies
the interlamellar regions the ion has axial symmetry and the symmetry axis is
perpendicular to the silicate layers (Figure 8A). The copper(1r) ion is most
likely co-ordinated to four water molecules in the xy plane and to two silicate
oxygens along the z-axis. Under conditions where two layers of water occupy
interlamellar regions the ion is in an axially elongated tetragonal field of 6
water molecules and the symmetry axis is inclined with respect to the silicate
layers at an angle near 45' (Figure 8B). If several layers of water molecules
%F
Silicate Layer
4
1
Silicate Layer
Figure 8 Schematic representation of the stereochemistry of hydrated copper(r1)

under conditions where (A) one layer and (B) two layers of water
occupy the interlamellar regions
(Reproduced by permission from J. Phys. Chern., 1973,77,196)
'06
'07
D. hf. Clementz, T. J. Pinnavaia, and M. M. Mortland,J. Phys. Chern., 1973,77,196.

J. P. Rupert, J . Phys. Chem., 1973,77, 784.
333
occupy interlamellar regions the [CU(H,O),]~+cation tumbles rapidly and
gives rise to a single isotopic em-. signal analogous to that normally observed
for the ion at temperatures above 50 K. Water monolayers were observed
with samples 1-6 whereas samples 6 and7 accommodatedtwolayers of water.
The e.s.r. spectra of interlamellar complexes formed between arene molecules
and copper(I1) montmorillonite CU~~,~(A~~~,M~,~,~)S~,O,~(OH)~
have also
been studied.707The spectra are interpreted in terms of the d9 copper(I1)
ions functioning as an electron acceptor for the transfer of a T-electron from
the arene molecule. Electron exchange may then occur between radical
cations or between radical and neutral diamagnetic species, resulting in the
single exchange-narrowed e m . band. Two types of arene complex (Types I
and 11 -terminology that of Mortland and P i n n a ~ a i a )were
~ ~ ~observed
*~~~
in the present study. Type I complexes, in which the arene ring remains
planar and the aromaticity is retained, were formed by benzene only; Type
11 complexes, which exhibit distortion of the arene ring and a loss of aromaticity, were formed with benzene, biphenyl, and anthracene.
A series of new leucite-type compounds has been synthesized by solidstate reactions in the temperature range 800-1 100 0C.710With the exception
of K,BeSi,O,,, which is tetragonal at ambient temperatures, a = 12.884,
b = 13.441 A, they all crystallize with cubic symmetry (Table 34). At elevated
Table 34 Lattice parameters
20 c
(ao/A)of synthetic
KzBeSi501z(420 C)
KZMgSi5012
KzZnSi,012
KZB2Si4012
CSzLio.~%.ssOll
CsZBeSi5Olz
CsZMgSi5OI2
13.212
13.396
13.373
12.645
13.598
13.432
13.823
leucite-type compounds at
Cs,CoSi501,
Cs2NiSi,012
CszCuSi,Olz
Cs,ZnSi,012
CszBzSi,Ol,
CszGazSi401z
13.683
13.632
13.621
13.679
13.030
13.731
temperatures, >400 C, K,BeSi,O,, also adopts a cubic structure (Table 34).

The crystal structure of the silicate Rb,Si,,O,,
(identical to Rb2Si,0g)
has been determined by means of three-dimensional X-ray single-crystal
studies;711itis orthorhombic [space group C2mm,a = 9.348(6), b = 16.290(7),
c = 8.055(5)A] and consists of a three-dimensional framework built up by
S O 4 tetrahedra sharing four as well as three corners. The arrangement of
tetrahedra can be derived from the tridymite structure and exhibits pseudohexagonal symmetry. The compound transforms into a high-temperature
modification with hexagonal symmetry (a = 9.45, c = 8.16 A) at 500 C.
Four papers describing the chemistry of aqueous solutions of sodium
708
08
710
M. M. Mortland and T. J. Pinnavaia, Nature, Phys. Sci., 1971,229, 75.

M. M. Mortland and T. J. Pinnavaia, J . Phys. Chern., 1971,75, 3957.
G. Bayer, Nuturwiss., 1973, 60, 102.
H. Schichl, H. Vollenkle, and A. Wittman, Monazsh., 1973, 104, 854.
334
silicates have been published during the period of this
Freund712,713
has studied these solutions using laser Raman spectroscopy,
within the composition range 0.33 < Na,O/SiO, < 3 mol 1-1 and for silica
concentrations greater than 0.3 moll-l. The structures of the monomeric
silicate anions are discussed and it has been demonstrated that the only
anions compatible with the spectroscopic studies are those derived from
orthosilicicacid Si(OH),, viz. SiO(OH)F, SiO,(OH)~-, Si03(OH)3-, and SiOt-.
The spectra of the anions SiO,(OH)g- and Si03(OH)3- have been assigned
completely. The structures of the polymeric anions have also been considered
with respect to the Na,0/Si02 ratio and the silica c o n ~ e n t r a t i o n A
.~~~~~~~
group of Russian workers have studied the equilibria in silicate solutions with
ionic strengths of 0.5,3.0,and 5.0mol 1-1 (maintained with NaCl) at 15-65
'C.'l4 The compositions of the silicate ions detected, which were similar to
those observed by
have been determined and the equilibrium
constants of the reactions (97)-(100) calculated. The changes in enthalpy
+ OH- + SiO(0H); + HzO

Si(OH), + 20H- + SiO,(OH); + 2Hz0
4Si(OH), + 20H- + Si40,(OH)6' + 6Hz0
4Si(OH)4 + 40H- + Si408(OH)f- + 8H20
Si(OH),
(97)
(98)
(99)
(100)
and entropy of these reactions have been estimated; those values obtained for
solutions with an ionic strength of 5.0 mol 1-1 are collated in Table 35.It was
Table 35 Thermodynamic parameters of silicate solution equilibrium
AG25 O C /
Reaction
(97)
(98)
(99)
kcal (g ion)-l
7.6 f 0.3
9.7 f 0.3
16.4 f 1.5
-AH/
kcal (g ion)-l
AS/cal
K-l (g ion)-l
1.0 f 0.5
1.5 f 0.5
3 f l
22 f 3
28 f 3
45 f 8
found qualitatively that an increase in temperature leads to a sharp decrease

in the stability of the tetranuclear silicate anion formed according to reaction
(100). An investigation specifically designed to consider the polymerization
of silicic acid in 0.084, 0.4, and 0.97 mol 1-1 aqueous HCl solution has been
undertaken using chemical, kinetic, and chromatographic methods by Hoebbe1 and Wieker.715It was observed that the condensation proceeds via the di-,
cyclotri-, cyclotetra-, and cyclohexa- or double-three-ring silicic acids, as
intermediates, leading to two-dimensional or three-dimensional high-molecular-weight silicic acids which are not of the known types, as double-chain
or phyllosilicate structures.
'I2
'I3
'I4
715
E. Freund, Bull. SOC.chim. France, 1973, 2238.

E. Freund, Bull. SOC.chim. France, 1973,2244.
I. Z. Pevzner, N. I. Eremin, N. N. Knyazleva, Yu. B. Rozen, and V. E. Mironov,
Russ. J . Inorg. Chem., 1973, 18, 596.
D. Hoebbel and W. Wieker, 2.anorg. Chem., 1973,400.148.
335
In a somewhat analogous study716 the equilibrium constants for the
formation of the dimer Si,86,- from SiOi- monomers in CuO-SiO, and
FeO-SiO, melts have been calculated from effective atomic charges and bond
energies; the values obtained are very similar to those obtained from experimental data.
The phenomenon of liquid immiscibility in silicate melts has been studied
both theoretically717and e~perimentally.~~~
The results of the theoretical
analysis717suggest that a criterion can be developed for the prediction of
liquid immiscibility in silicate melts; several examples of liquid immiscibility
gaps were observed in an experimental i n v e s t i g a t i ~ n . ~ ~ ~
The enthalpies of formation of a number of crystalline silicates have been
or ~ x i d e - m e l solution
t ~ ~ ~ calorimdetermined by either aqueous HC1719-721
etry; they are summarized in Table 36.
Table 36 Enthalpies of formationlkcal mol-l of complex silicates
Ref.
Ba2ZrzSi,012
Na,Zr,Si4015
Nal4Zr2SilooS1
Ca,SiO,Cl,
MgSiO, (pyroxene)
Mg,SiO, (olivine)
Al,SiO, (sillimanite)
Al,SiO, (kyanite)
-1537.1
-1898.5
-3854.5
-746.9
$8.12 f 0.21
-14.99 f 0.15
-1.1 f 0.3
+0.75 f 0.26
719
720
720
72 1
722
722
722
722
Surprisingly few investigations of the reactivity of silicates have been

carried out. Thompson723has refuted the recent suggestion of Ramachandran
and Sereda7,*that a part of crystalline tricalcium silicate, Ca,SiO,, is chemically different from and more reactive than the remainder; it is pointed out
that by slightly different conditioning of the starting silicate, very different
chemistry is observed. As part of a wider study of the hydration of tricalcium
silicate, Ca,SiO,, and p-dicalcium silicate, Ca2Si04,725the reaction mechanism of the acceleration of the process by CO, treatment has beeninvestigated.
It is concluded that the predominant chemical reactions occurring on carbonation are:
Ca,SiO,
Ca,SiO,
716
717
718
'19
720
721
722
723
72p
+ yHaO + (3 - x ) C 0 2 -+ xCaSiO,,yH,O + (3 - x)CaCO,

+ yH,O + ( 2 - x)CO, -+ xCaSiO,,yH,O + (2 - x)CaCO,
0. A. Esin, Rum. J . Phys. Chern., 1972, 46, 132.

K. L. Currie, Nature, Phys. Sci., 1972,240, 66.
P. J. Massion and A. F. Koster van Groos, Nature, Phys. Sci., 1973, 245, 60.
E. V. Shibanov and V. G. Chukhlantsev, R i m . J . Phys. Chem., 1972,46, 1539.
E. V. Shibanov, V. G . Chukhlantsev, and K. V. Alyamouskaya, Russ. J . Phys. Chem.,
1972,46, 617.
E. V. Shibanov and V. G. Chukhlantsev, Russ. J . Phys. Chem., 1972,46,617.
J. A. Shearer and 0. J. Kleppa, J . Inorg. Nuclear Chem., 1973, 35, 1073.
R. A. Thompson, Nature, Phys. Sci., 1972,240, 119.
V. S. Ramachandran and P. J. Sereda, Nature, Phys. Sci., 1971,233, 131.
R. L. Berger, J. F. Young, and K. Leung, Nature, Phys. Sci., 1972,240,16.
336
The influence of sodium and potassium silicate melts (K,Si,O,, K2Si,05,

K2Si03,Na,Si,O,, Na2Si,05, and Na,SiO,) on silicon nitride Si3N4has been
assessed.726The interactions between Si3N4and the cited silicates are described
by general equations and it is concluded that articles made from Si3N, are
unsuitable for use with sodium and potassium silicate melts.
A number of properties of Cs,ZrSi,O,, Cs4Zr2Si,0,,, and Cs,ZrSi,O,
have been
Whereas both Cs,ZrSi,O, and Cs4Zr2Si,0,, are decomposed by water at 320-340 C, CsZrSi,O, is stable; this latter silicate is
also more thermally stable than the other two - at 850 OC all three are stable
but at 127OoC Cs,ZrSi,O, and Cs4Zr2Si5016rapidly lose Cs,O. All three
silicates are decomposed by solutions of strong mineral acids.
Phase equilibria in several silicate-containing systems have been investigated; the results are summarized in Table 37.728-734
TabIe 37 Phase equilibria in silicate-containing systems

Systems studied
BaSi0,-Nd,SiO,
MgSiO,-Nd,SiO,
Ba0-CaGGe0,-SiO2
Pb0-PbS04-PbSi03
Pb0-PbCr0,-PbSiOs
Li,0-Sc20,-Si0,-H20
Ca2Si04-Ca2Ge04-H20
Phases, other than terminal, observed
Ref.
Apatite-type phases in the concentration

range 56-72 mole% NdzSi05
Ca2SiOp,Ba,SiO,, Ca,GeO,, Ba,GeO,
-
728
729
730
73 1
732
733
LiScSiO,, Li2SiOs, Li2Si205,LiScOz
734
(iii) Ahminosilicates. The reader is advised that a second discussion of the

chemistry of the aluminosilicates described during the period of this Report,
which is complementary to that given here, is to be found in Chapter 3
(Section 2). A review of the hydrothermal method for the artificial growth of
crystals has been compiled by Kuznetsov and lob ache^;^,^ included in the
review is a detailed consideration of the growth of aluminosilicates. B a ~ r ~ ~ ~
has recently put forward the argument that N3- may substitute for 0,-in
aluminosilicates. (Previously nitrogen has always been thought to be present
in these systems as the NHZ ion, substituting for alkali-metal cations). The
proposal is based on the fact that solid solutions of aluminium-silicon oxide
A. I. Kulikov, Zzvest. Akad. Nauk S.S.S.R.,Neorg. Materialy, 1973, 8,604.
K. V. Alyamovskaya and V. G. Chukhlantsev, Russ. J. Inorg. Chem., 1972,17, 965.
728 N. F. Fedorov, I. F. Andreev, and T. A. Tunk, Russ. J. Inorg. Chem., 1972, 17,282.
72Q N. F. Fedorov, I. F. Andreev, and T. A. Tunk, Russ. J. Inorg. Chem., 1973,18,421.
730 R. G. Grebenshchikov and V. 1. Shitova, R u n . J . Inorg. Chem., 1972, 17, 1487.
731 V. M. Manakov, G. A. Bukhalova, and V. T. Maltsev, Rum. J. Znorg. Chem., 1972,
17,276.
732 V. T. Maltsev, G. A. Bukhalova, and V. M. Manakov, Rum. J. Inorg. Chem., 1972,
17,278.
733 N. S. Koryakina, V. A. Kuznetsov, and N. V. Belov, Soviet Phys. Cryst., 1972, 17,
191.
7 3 4 A. K. Shirvinskaya and I. A. Bondar, Doklady Chem., 1972,202, 161.
735 V. A. Kuznetsov and A. N. Lobachev, Soviet Phys. Cryst., 1973, 17,775.
736 W. H. Baur, Nature, 1972, 240,461.
728
727
337
nitride S i ( 6 - o . , ~ ~ A l o . 6 , ~(0o Q
~N
x (<
~~
5 )~have been prepared,737indicating
that the nature of the Si-N and Al-N bonds must be similar to the character
of the Si-0 and A1-0 bonds.
A number of structural investigations of naturally occurringaluminosilicates
and borosilicates have been undertaken. Single-crystal X-ray diffraction
studies of m e i ~ n i t e , s~~~a~p o l i t e , l~e~p ~i d ~ l i t e , anortho~lase,7~~
~~~
and
garrel~ite'~~
specimens have been described. The crystal structures of the two
natural minerals which approximate most closely to the idealized end
members of the solid-solution series; marialite (Na,AI,Si,O,CI)
to
meionite [Ca4A&Si60,4(C03)], have been determined and a n a l y ~ e d . ~ ~ ~ ~
M e i ~ n i t e , of
~ ~ ~unit-cell formula (Ca7~,,Nao~39KO~lgFeo~038Mgo~o,Sro~o,,)
Table 38 Lattice parameters 0f 2M2 lepidolites
lepidolite from Elba
lepidolite from Rozna
a/A
b/A
CIA
9.04
9.032
5.22
5.20
20.210
20.15
Spacegroup
99'35'
99'46'
C2/c
C2/c
.33)048.51c10. 053(s04)0,053(c03)1.
895 Y has been shown to be tetragonal, space group P4,/n, with unit-cell parameters a = 12.194, c = 7.557 A.
The structure is similar to that of marialite but with significant differences in
atomic co-ordinates and aluminium site occupancies. The CO, groups are
essentially disordered on the (001) plane and the calcium cation is eightrather than six-co-ordinate. The crystal structure of a scapolite ~ a r n p l e , 7 ~ ~
(N a5. 76
.67 KO. 42 e0.003
"0.005 rO .002) (si16.68 A17. 34) O48.55 Ic11.45 (sO4)O.007
(cO3)0.44] which approximates most closely to marialite has been refined in
the newly determined tetragonal space group P4Jn;the unit-cell parameters
are very similar to those of the sample of meionite, a = 12.059, c = 7.587 A.
The refined structure has been found to be similar to that previously reported
but has a different symmetry, with significant difference in the aluminium
distribution and the co-ordinates of some sites, especially the (Na, Ca) site.
The crystal structure of a natural sample of a 2M, lepidolite (a mica-type
mineral)740from the island of Elba (Italy) has been determined by singlecrystal X-ray diffraction techniques and compared with that of a second
2M2 l e p i d ~ l i t efrom
~ ~ ~Rozna (Czechoslovakia) and other related structures.
The two sets of unit-cell parameters are collated in Table 38. The most
interesting features which emerge from the comparison74oare the constant
presence of remarkable octahedral ordering and the almost identical composition of the tetrahedral sheets (Elba: Si3.36A10.64;Rozna : Si3.39Alo.61)
(si12 .41A111
737
738
740
741
742
743
K. H. Jack and W. I. Wilson, Nature, Phys. Sci., 1972,238,28.

S. B. Lin and B. J. Burley, Acta Cryst., 1973, B29, 2024.
S. B. Lin and B. J. Burley, Acta Cryst., 1973, B29, 1272.
F. Sartori, M. Franzini, and S. Merlino, Acta Cryst., 1973, B29, 573.
R. De Pieri and S. Quareni, Acta Cryst., 1973, B29, 1483.
S. Ghose and H. Ulbrich, Naturwiss., 1973, 60, 349.
1. Takeda, N. Haga, and R. Sadanaga. Mineral J., 1969, 6 , 102
338
Inorganic Chemistry of the Main-group Elenrents
which are made up by tetrahedra distorted into a form near to that of an
elongated pyramid.
The structural analysis of an a n o r t h ~ c l a s ean
, ~ intermediate
~~
alkali-metal
feldspar (Na, K)AlSi,O,, has shown that there is complete disorder in the
Si-A1 distributions and that the framework of tetrahedra is perfectly analogous to that in the high-temperature form of albite. The Si-A1 distribution in
fibrolite, the fine-grained variety of sillimanite Al,SiO,, has also been the
subject of discussion. The statement of Cameron and A s ~ o r t hthat
~ ~the
Si-A1 distribution is ordered is criticized in its general form by Sahl and
Seifert,745it being argued that the experimental results put forward as indicating Si-A1 ordering do not, in reality necessarily imply that this occurs.
The crystal structure of the borosilicate g a r r e l ~ i t eNaBa3Si,B,016(OH),,
,~~~
has been shown to be monoclinic, space group Cc or C2/c, with unit-cell
parameters a = 14.639, b = 8.466, c = 13.438 8,; = 114.21. The threedimensional structure is based on two components; the first consists of slabs of
Ba-0 polyhedra parallel to (0011, linked together by sharing edges and faces,
whereas the second consists of borosilicate chains running parallel to (1 10).
The latter contains two types of tetrahedral four-membered rings whose
planes are at right angles to each other; each ring is composed of two silicate
and two borate tetrahedra, the silicate tetrahedra being common to the two
types of four-membered rings.
The tubular structure of imogolite, a hydrated aluminosilicate, has been
analysed from the results of electron diffraction, electron microscopy, and
chemical investigation^.^^^ (X-Ray structural analysis is very difficult for this
mineral because of the diffuse nature of the crystal data). Electron microscopy has shown the mineral to consist of bundles of fine tubes each ca. 20 A
in diameter; electron-diffraction data and chemical analysis suggest that the
structure is based on gibbsite units with tetrahedral SiO, units. Accordingly,
three trial structures with circumferences of 10, 11, and 12 gibbsite unit cells
were proposed for imogolite based on the insertion of an orthosilicate anion
into a gibbsite sheet by displacing hydrogen from the three OH groups
surrounding a vacant octahedral site, the fourth Si-0 bond pointing away
from the sheet and being neutralized by a proton to form Si-OH; this gives
a composition (OH)3Al,03SiOH, which is similar to the quoted empirical
formulae. The calculated diffraction data for all three models were in reasonable agreement with the experimentally determined data; it was thus concluded that the model structures are correct in principle.
A lH n.m.r. investigation of both single-crystal and polycrystalline samples
of hydrosodalite Na4[A13Si3012](OH),3H20has been ~ndertaken;~,on the
basis of a detailed analysis of the spectra, a model has been proposed for
744
745
747
W. E. Cameron and J. R. Asworth, Nature, Phys. Sci., 1972,235, 134.

K. Sahl and F. Seifert, Nature, P h p . Sci., 1973, 241, 47.
P. D. G. Cradwick, V. C. Farmer, J. D. Russell, C. R. Masson, K. Wada, and N.
Yoshinaga, Nature, Phys. Sci., 1972,240, 187.
V. Yu. Galitskii, V. N. Shcherbakov, and S. P. Gabuda, Soviet Phys. Cryst., 1973,17,
691.
339
hydrosodalite in which the water molecules and OH groups are statistically
distributed in the octuple positions of the structures. It has also been established from a study of the Mossbauer effect of the 57Fenuclei in biotite748
that there are two non-equivalent positions occupied by the Fe2+cationsin the
structure; these correspond to the cis and trans octahedra.
Several synthetic alumino-, boro-, and gallo-silicates have been prepared
and characterized; they include RbA1Si04,749
MGaSi04750(M = Li, K, Rb,
Li3A1Si05,752
(FeII', AI),Si05,753and (V"', A1),Si05.753
or Cs), Sr0.5BSi04,751
RbA1Si0,749was prepared by hydrothermal synthesis; it has been shown to be
isostructural with CsAlSiO, (Table 39). The gallosilicates MGaSi04750were
Table 39 Lattice parameterslK of RbAlSiO,, CsAlSiO,, and Sr,.,BSiO,

Compound
RbAlSiO,
CsAlSiO,
Sr.,,BSiO,
9.22
9.44
8.187
5.33
5.45
8.948
8.74
8.90
7.957
prepared by heating stoicheiometric amounts of gallium hydroxide and the

alkali-metal disilicate in the temperature range 800-1200 "C for from 70 to
190 hours. Sro.5BSi0251was prepared by heating intimate mixtures of SrCO,,
SO2, and H,BO, in a hydrogen-nitrogen atmosphere at 600-1000 'C. It was
found to be isomorphous with danburite, Ca,,,BSiO,; the orthorhombic
structural parameters of Si0.,BSiO4 are compared with those of RbAlSiO,
and CsAlSiO, in Table 39. SrO.,BSiO4,christened strontium danburite, was
synthesized as part of a wider study of the luminescence of Eu2+-activated
aluminosilicate. The activated material (max. Eu content, ca. 5 %) was
prepared by addition of Eu203to the previously described reaction mixture.
Li3AlSi0252has been prepared by sintering Li,O-Al,O,-SiO,
mixtures with
Li,C03. The d.t.a. of the product showed an endothermic effect at 11851225 'C. specimens of Li,AlSiO, quenched from 1200 'C consist of minor
amounts of the high-temperature modification of 7-LiAlO, and Li,SiO,.
Iron- and vanadium-bearing kyanites (Fe'", Al)SiO, and (V'I', Al)Si0,753
have been synthesized at 900 and 1000C under high pressures. Solid solubility on the pseudobinary sections A1,Si05-Fe,Si05 (or V2Si05) of the
A1,03-Fe,0, (or V203)-Si0, systems is up to 6.5 mole % (or 14 mole %)
of the theoretical end-member Fe,SiO, (or V,SiO,) at 900 "C and 20 kbar748
74s
750
751
75a
753
E. V. Pol'shin, V. I. Matyash, V. E. Tepikin, and V. P. Ivanitskii, Soviet Phys.

Cryst., 1972, 17,278.
R. Klaska and 0. Jarchow. Naturwiss.. 1973. 60.299.
A. S. Berger, T. 1. Samsonova, and I. A.Poroshina, Russ. J. IHorg. Chem., 1972,17,
643.
J. M. P. J. Verstegen, J. W. Ter-Gruft, and W. L. Wanmaker, J. Inorg. Nuclear Chem.,
1972,34,3588.
Z . S . Tkacheva and L. K. Yakovlev, Izvest. sibirsk. Otdel. Akad. Nauk S.S.S.R., Ser.
khim. Nauk., 1972,73.
K. Langer and K. R. Frentrup, Contrib. Mineral Petrology, 1973, 41, 31.
23
340
For bulk compositions with higher Fe2Si0, (V2Si05)contents the corundumtype phases Fe,03 (V20,) coexist with the appropriate saturated kyanite
solid solution plus quartz.
Several authors have reported the results of experiments involving the
reactions of a l u m i n o ~ i l i c a t e sA. ~physicochemical
~~~~~
study of the reaction
between synthetic /3-eucryptite (LiAlSiO,) and Li,C0,754 has established that
when the molar proportions of the reactants are ~-LiAlSiO,:Li,CO, = 1:
0.25-2.0, a trilithium aluminosilicate Li3A1Si0, is formed. The solid-state
Table 40 Zeolite phases observed as products of hydrothermal reactions
of nzetakaolinite
phillipsite
gismondite
gmelinite
chabazite
faujasite
Linde A type
sodalite
cancrinitehydrates
lithium zeolites (2)
sodium tetramethyl-
reactions of Egyptian kaolin, Al,Si,O,(OH),, and

and Ni0756have
been examined; the effects of the three parameters concentration, particle
size, and temperature have been assessed from spectrophotometric and X-ray
diffractometric analyses of the reaction products. The results show that the
appropriate spinel CoAl,O, or NiAl,O, is formed together with free silica
and mullite, Al,Si,Ol3; these are analogous to the previous results of the
kaolin-CuO system.
A comprehensive report describing the reactions of metakaolinite, A12Si,0,,
with single and mixed bases has been published by Barrer and M a i n ~ a r i n g . ~ ~ ~
The low-temperature hydrothermal reactions of metakaolinite were studied
with and without additions of silica by use of the bases LiOH, NaOH, RbOH,
and CsOH and also the mixtures NaOH LiOH, NaOH KOH, KOH
LiOH, and NaOH + Me,NOH. Over certain temperature and composition
ranges, reproducible crystallizationfields have been obtained for all the above
bases and pairs of bases. Two hydrated non-zeolites were formed, nepheline
hydrate and a near hectorite, and also a group of anhydrous phases. Under the
conditions employed, however, zeolitization reactions were dominant, which
are largely but not fully paralleled by similar reactions in aqueous alkaline
aluminosilicate gels. A number of the products have been characterized
using physicochemicaltechniques such as X-ray diffraction, t .g.a.,and sorption
studies. The most frequently occurring zeolite phases were those related to
those tabulated in Table 40.
754
755
756
757
758
Z. Stkacheva and L. K. Yakovlev, Russ. J. Inorg. Chem., 1973,18, 358.

M. Hassanein and S. El-Sawy, 2.anorg. Chem., 1973,399,251.
M. Hassanein and S. El-Sawy, 2.anorg. Chem., 1973,396,328.
R. M. Barrer and D. E. Mainwaring,J.C.S. Dalton, 1972,2534.
Ya. Baukr and D. Rykl, Soviet Phys. Cryst., 1972, 17, 615.
341
The processes involved in the decomposition of natural beryl (B~Al,Si,O,,)
in NaOH solutions under hydrothermal conditions have been investigated758
The predominant product of the reactions, which were carried out at 400,
500, and 600 C,was found to be chkalovite, Na2BeSi20,. In the crystalline
crusts which developed on the beryl, kaolinite and sometimes nacrite,
lochmite, and hydrargillite were formed. Besides chkalovite, the beryllium
minerals included bavenite, milarite, and sometimes bertrandite; in one
experiment trimerite was formed.
Phase relationships in the two systems Na20-Ca0-A1,0,-Si0~59 and
CaMgSi20,-CaA1,Si0,7s0 have been defined, and the stability diagrams of
some clay minerals in aqueous solutions deterrnined.7,l
(iu) Zeolites. A comprehensive review of the chemistry of zeolites entitled
iMolecular Sieves has been compiled by Meir and U y t t e r h ~ e v e nthe
; ~ ~speci~
fic aspects of zeolite chemistry considered have been grouped under the subheadings: structure; crystallization; ion exchange and modification; adsorption and catalysis. The zeolite literature abstracted for the present Report,
however, has been restricted to those papers which discuss the preparation,
characterization, or structural analysis (of both the crystal and its surface)
of zeolites ;those reports describing solely the ion-exchange, adsorption, and
catalytic properties of the zeolites have not been included.
A short review has been published by T s i t ~ i s h v i lin
i ~which
~ ~ the structures
of porous zeolites, their porosities, surfaces, types of lattice, and the effect of
chemical modification on their adsorption, chromatographic, spectroscopic,
and catalytic properties have been examined. The effect of the nature of the
cations on the properties of the zeolites has also been discussed.
Zeolitization reactions have been found to predominate in the low-temperature hydrothermal reactions of metakaolinite, A12Siz0,.764The reactions
have been carried out with and without additions of silica by use of bases
LiOH, NaOH, RbOH, and CsOH and also the mixtures NaOH LiOH,
NaOH KOH, KOM LiOH, and NaOH
Me,NOH. The zeolites
produced, which have been characterized by a number of physicochemical
techniques, have been listed in the section on aluminosilicates (Table 40).
The synthesis of the zeolites Linde A and faujasite has been studied using
phosphorescence spectroscopy and laser Raman spectroscopy ;765 the results
obtained were indicative of a zeolite crystallization in the solid gel phase via
condensation between hydroxylated Si-A1 tetrahedra.
Seff et aZ.766-768have once again reported the fascinating results obtained
759
780
763
783
784
765
786
787
R. Dinesch and M. Cerchez, Rev. Roumaine Chim., 1973,18, 23.

K. Hijikata, J . Fac. Sci.Hokkaido Univ., Ser. 4, 1973, 16, 167.
W. H. Huang, Nature, Phys. Sci., 1973,243, 35.
W. M. Meir and J. B. Uytterhoeven, Adv. Chem. Ser., 1973, Vol. 121.
G. V. Tsitsishvili, Russ. J . Phys. Chem., 1972, 46, 1723.
R. M. Barrer and D. E. Mainwaring, J.C.S. Dalton, 1972, 2534.
B. D. McNichol, G. T. Pott, and K. R. Luds, J. Phys. Chem., 1972,76,3388.
R. Y.Yanagida and K. Seff, J. Phys. Chem., 1973,77, 138.
A. A. Amaro and K. Seff, J.C.S. Chem. Comm., 1972, 1201.
A, A. Amaro and K. Seff, J . Phys. Chem., 1973,77,906.
342
from single-crystal X-ray diffraction studies of both

and acetylene767,768
sorption complexes of zeolite NaA. In an attempt to determine
either the most favourable of the four sorption sites (maximum occupancy
8, 4, 8, 12 ammonia molecules) of the zeolite NaA, of unit-cell stoicheiometry Na12Al12Si12048,at lesser loadings than the nearly filled 32ammonia
c0mplex,7~~
or the site selected by the first molecules to enter each unit cell,
the 8ammonia complex was prepared766and studied by crystallographic
procedures similar to those described previously.769The resulting complex
was found to be cubic, with space group Pm3m and cell constant a =
12.289(5) A. From an analysis of the data it appears that at this loading the
sorbed molecules are not predominantly found at one kind of sorption site.
It is suggested that it is possible that all three kinds of Na+ compete favourably at room temperature for ammonia association at all sites where further
bonding can occur to framework oxygen atoms. This result is consistent with
the complete absence of any indication of the existence of a plateau or of
unevenness in the sorption isotherm of the 32ammonia complex. Fully
vacuum-dehydrated zeolite NaA of the same approximate composition was
exposed to dry acetylene for 24 hours at 650 Torr
The acetylene
sorption complex was found to be cubic with space group Pm3m and cell
constant 12.260(5)A. Approximately six acetylene molecules are sorbed per
unit cell under these conditions; they are found associated with Na+ ions at
three non-equivalent sorption sites in the zeolite NaA structure. In each
case the Naf cation approaches the acetylene molecule equatorially, indicating
that the principal interaction is between cation charge and the laterally
polarizable m-electron system of the unsaturated hydrocarbon.
Seff et a2.770*771
have also determined the crystal structures of fully dehydrated partially C ~ ~ f - e x c h a n g eand
d ~ ~both
~
hydrated and fully dehydrated partially Mn2+-exchangedzeolite NaA.771Single crystals of zeolite
NaA, of unit-cell formula Na12A112Sil,048,xH20,were subjected to ion
exchange in 0.1 mol 1-1 aqueous cobalt(@ nitrate solution at 75 OC for three
weeks.77oAfter analysis, back-exchange using a measured amount of unexchanged zeolite NaA was conducted to give samples containing four Co"
ions per unit cell. The single crystal was dehydrated at
Torr and 350 "C
for 48 hours and X-ray diffraction studies were carried out. It was observed
that the CoI' ions occupy three-fold axis sites near the six oxygen windows
(Figure 9), each CoII ion being 2.06(1)A from three trigonally arranged
equivalent oxygen atoms. The OCoO angle is 119.4', close to the equilateral
trigonal planar angle, 120'. Single crystals of zeolite NaA of the same
composition were allowed to exchange with excess 0.1 rno1I-l Mn(C104)2
solution at ca. 28 'C for three months.771Chemical analysis of the exchanged
zeolite revealed 4.5 Mn" ions per unit cell, the unit-cell stoicheiometry being
Mn4~,Na,Al12Si1204,,xH,0.
X-Ray diffraction data were collected for both
76@
"O
"l
R. Y. Yanagida and K. Seff, J. Phys. Chem., 1972,76,2597.

P. E. Riley and K. Seff,J.C.S. Chem. Comm., 1972, 1287.
R. Y. Yanagida, T. B. Vance, and K. Seff,J.C.S. Chem. Comm., 1973,382.
343
Figure 9 The unit cell of partially Co(I1)-exchangedfully dehydrated zeolite

NaA. The near trigonal-planar co-ordination of the C O ( I Iions
)
is
indicated by dashed lines. Sodium ion co-ordination is indicated by
dotted lines
(Reproduced from J.C.S. Chem. Comm.,1972, 1287)
hydrated and dehydrated crystals. In both structures the Mn" ions occupy
three-fold axis sites near the six-oxygen windows; (cf. the CoI'-exchanged
zeolite NaA, Figure 9); they are recessed a small amount in both hydrated
[0.24(3) A] and dehydrated [0.11(3) A] crystals from the plane into the large
cavity. In the dehydrated structure each Mn'I ion is 2.11 A from three trigonally arranged oxygen atoms, the OMnO angle being 119.6", close to the
trigonally planar angle 120' (Figure lOa) (cf. the dehydrated Co'I-exchanged
zeolite NaA). In the hydrated structure, however, the MnI' ions are pentaco-ordinate in a trigonal-bipyramidal manner, the axial ligands being two
non-equivalent water molecules (Figure lob). The Mn'I-OH,
distances are
(a)
(b)
Figure 10 Equivalent Mn(11)-occupied six-oxygen windows of Mn(u)-exchanged
dehydrated zeolite NaA (a) and of the corresponding hydrated
structure (b). The co-ordination about the Mn(I1) ions is indicated
by heavy lines
(Reproduced from J.C.S. Chem. Comm., 1973, 382)
344
approximately equal at 2.03(6) and 2.06(7)1$ for H,O(I) and H,O(2),
respectively. The three equivalent equatorial framework oxygen atoms are
2.28 A from the MnI ions, affording these ions nearly regular bipyramidal
co-ordination.
The variation of the i.r. spectra, structure, and related properties of aluminium-free forms of zeolite L has been measured as a function of its decationization effected with HCI at different concentration^.^^^
Because of the difficulty in interpreting X-ray data of zeolites and related
compounds when more than one type of cation is present in the zeolite (since
essentially the same electron-density distribution may result from different
cation arrangements), a number of investigations have been undertaken to
provide alternative means of studying cation l o c a t i ~ nA. theoretical
~ ~ ~ ~ ~ ~
discussion of the cation distribution in Y-type zeolites773has led to the proposal of an ionic-covalent model of the zeolite crystal which permits the
prediction of the cation distribution order in the structure which is basically
in agreement with the experimental data. The location of Ni2+ cations in
nickel-exchangedNaA, NaX, and NaY zeolites has been studied by hydrogensorption
magnetic measurements,776and X-ray-diffraction
By measuring the rate of uptake of hydrogen by NaNiX zeolites at
different extents of exchange it was anticipated that different reaction rates
corresponding to different crystallographicenvironments for the cations might
be d i ~ t i n g u i s h e dFrom
. ~ ~ ~ an analysis of the results it was not possible to
differentiate between any of the sites adopted by the exchanged nickel cations.
The bulk susceptibilities of nickel-exchanged forms of zeolite A, X, and Y
have been measured as a function of temperature for both hydrated and
dehydrated zeolites.775In fully hydrated zeolites the magnetic measurements
indicate that the Niw ions are octahedrally co-ordinated. On dehydration,
the octahedral co-ordination is retained by the Ni2+ions of NiA and NiCaX;
fully dehydrated NiA was found to be unstable. In the case of NiX and NiY
zeolites, dehydration causes a decrease in co-ordination around the Ni2+
ions, firstly to a distorted octahedral or pentahedral co-ordination, followed
by tetrahedral co-ordination where three of the ligands are lattice oxygen and
the fourth derived from residual H,O. The crystal structures of three nickelexchanged NaY zeolites have been studied using X-ray diffraction in order to
estimate the location of and population of different cation sites as a function
of both exchange and level of dehydration.77sIn summarizing the results it
has been found that on progressive removal of water molecules, Ni2+ ions
771
773
774
775
776
777
778
77p
L. P. Shirinskaya, N. F. Ermolenko,N. P. Kulikovskaya,V. Ya. Nikolina, and N. P.

Pryakhina, Russ. J. Phys. Chem., 1972, 46,77.
M. N. Zhavoronkov, J . Struct. Chem., 1972, 13, 312.
A. C . Herd and C . G. Pope, J.C.S. Faraday, I , 1973,69, 833.
T. A. Egerton and J. C. Vickerman, J.C.S. Furaday I , 1973, 69, 39.
P. Gallezot and B. Imelik, J . Phys. Chem., 1973,77, 652.
I. R. Leith and H. F. Leach, Proc. Roy. SOC.,1972, A330,247.
C.-C. Chao and J. H. Lunsford, J . Chem. Phys., 1972,57,2890.
E. E. Dilmukhambetov, A. V. Kiselev, N. M. Kuzmenko, V. I. Lygin, and M. A.
Shubaeva, Russ. J . Phys. Chem., 1973, 46, 144.
345
enter the hexagonal prisms but that their population is limited to twelve Ni2+
ions per unit cell. A correlation between the population of Ni2+ cations in
hexagonal prisms, the cubic unit-cell constant, and the total number of Ni2+
cations has also been proposed.
E.p.r.777*77s
and U . V . " ~ spectroscopic analyses have been applied to an
assessment of the positions of Ca2+ cations in copper-exchanged NaX777
and NaY778n779
zeolites. E.p.r. spectra of dehydrated copper-exchanged X-type
zeolite have been obtained which suggest that the Cu2+ions are distributed in
at least two magnetically non-equivalent environments.777Cu2+ ions in one
of these environments exhibit a preferential reactivity towards a variety of
simple molecules. It is postulated that these cations are located in sites 11' in
the sodalite cage whereas the less reactive cations are in relatively inaccessible
sites I' which are displaced slightly into the sodalite cage from the hexagonal
prism joining together the two sodalite units. In a separate investigation of
the e.p.r. spectra of copper-exchanged Y-type zeolites, the structures of
identical and non-linear Cu2+ pairs present in these materials have been
a n a l y ~ e dThe
. ~ ~identical
~
pairs are formed by exchange-coupled Cu2+ ions
which have the same symmetry axis and magnetic parameters; they are
formed by coexchanging Cu2+ with Mg2+, Ca2+, or La3+ ions into a NaY
zeolite. The non-linear pairs which are formed on more extensive Cu2+
exchange have symmetry axes that form an angle of 110' with respect to each
other. These models compare favourably with available X-ray-diffraction
data on CuY zeolites. The spectrum of the transitions in the d-electron system
of CuNaY zeolite evacuated at 70C has been shown to be analogous to
that of the hexa-aquo-copper complex.779The change in the spectrum observed on further dehydration by heating from 70 to 200 "C has been accounted for by the formation of surface copper complexes with a tetragonally distorted octahedral or square-pyramidal structure in which the ligands are
both water molecules and oxygen ions from the zeolite framework. The
change in spectrum at higher temperatures is thought to be associated with
incorporation of copper(@ cations into the zeolite framework.
The mobility780and self-diffu~ion~~~
of zinc in faujasite-type synthetic
zeolites NaX and NaY have been investigated as part of a wider series of
investigations of these zeolites.
Considerable interest has been shown recently in the chemistry of species
adsorbed on zeolite surfaces. For example, a Raman spectroscopic investigation of zeolites and the molecules adsorbed thereon has been undertaken.7s2
All the zeolites examined give weak Raman spectra; in nearly all cases the
samples gave rise to an excessive background, and in order to minimize the
problem it was necessary to use high-purity materials. Although these spectra
are not as informative as the i.r. framework frequencies, they still show
differences between zeolite structures. The Raman spectra of adsorbed
780
781
788
A. Dyer and R. P. Townsend, J . Inorg. Nuclear Chem., 1973,35,2993.

A. Dyer and R. P. Townsend, J . Znorg. Nuclear Chem., 1973, 35, 3001.
C. L. Angell, J . Phys. Chem., 1973,77,222.
346
molecules (CO,, propylene, acetonitrile, and acrolein) on zeolites NaA,
NaX, NaY ,and NH4Y have also been determined. In each case the spectrum
resembled that of the liquid state, indicating that in all of these samples only
physical adsorption had occurred. An examination of the effect of unsaturated
hydrocarbon adsorption on the unit-cell constants of NaY and protonexchanged NaY zeolites has also been effected.7s3By determining the unit-cell
constant of these zeolites as a function of exchange (Nay, Na,,H,,Y, and
Na,H,,Y were the zeolites considered) and hydrocarbon adsorption it has
been concluded that the interaction between the unsaturated molecules
adsorbed on the zeolite and the Na+ cations is the main cause for the observed
decrease in the unit-cell constant.
More specificinvestigations of the species adsorbed on zeolites have studied
deut eriot oluene,793 amm0nia79287~~*
'95
oxygen,7&p-786 wat er ,787-791propylene,792
nitrogen oxides,796*797
carbon monoxide.798and carbon dioxide799as the
sorbed molecules. Three groups of authors have studied the adsorption of
oxygen on zeolite surfaces.78p786An e.s.r. spectroscopic investigation of the
thermal formation of oxygen radicals on Y-type zeolites has shown that two
different radicals were formed on NaY and LiY zeolites but not on KY
zeolites.7s4The first radical is the superoxide ion 0;adsorbed on the alkalimetal cations and similar to that already known to be formed by y-irradiation.
The second radical, which was formed only on the NaY and LiY zeolites,
was favoured at higher temperatures and distinctly increased in concentration
on adding transition-metal cations to the sample; in fact, in the absence of
these cations the second radical was not observed. It was also found only at
high levels of Naf or Li+ (or at low concentrations of H+) on the zeolite
surface. These and further observations indicated that the transition-metal
cations (e.g. Fe2f or Cu2+)act as electron donors which promote formation
of the oxygen radicals by an electron-transfer mechanism. Since the species
was stable at 500 "Cin uacuo it was concluded that it must have strong bonding
with the zeolite surface; it was further suggested that this oxygen species is
P. Gallezot and B. Imelik, J. Phys. Chem., 1973,77,2764.
T. Imai and H. W. Habgood, J. Phys. Chem., 1973,77,925.
785 Y . B. Taarit and J. H. Lunsford, J. Phys. Chern., 1973,77, 780.
786 J. C. Vedrine and C. Naccache, J . Chem. Phys., 1973, 77, 1606.
787 P. A. Jacobs and J. B. Uytterhoeven, J.C.S. Faraday I, 1973, 69, 359.
7 8 8 P. A. Jacobs and J. B. Uytterhoeven, J.C.S. Faraday I, 1973, 69, 373.
7 8 9 A. V. Kiselev, V. I. Lygin, and R. V. Starodubceva, J.C.S. Furaday I , 1972,68, 1793.
7 9 0 A. A. Kubasov, A. N. Ratov, I. V. Arkhanoel'skii, K. V. Topchieva, and E. N .
Rosolovskaya, Russ. J . Phys. Chem., 1972,46, 1693.
7g1 B.-H. Ha and D. Barthomeuf, Bull. SOC.chim. France, 1973, 1869.
782 D. F. Best, R. W. Larson, and C. L. Angell, J . Phys. Chem., 1973,77,2183.
7D3 V. V. Berentsveig, A. P. Rudenko, and A. A. Kubasov, Doklady Chem., 1972, 204,
783
783
784
795
796
797
798
799
460.
A. V. Kiselev, N. M. Kuz'menko,and V. I. Lygin, Russ. J. Phys. Chem., 1973,47,88.
Y. Huang and E. F. Vasant, J. Phys. Chern., 1973, 77,663.
C. Naccache and Y. Ben Taarit, J.C.S. Faraday I, 1973, 69, 1475.
P. H. Kasai and R. J. Bishop, J. Phys. Chem., 1973,77,2308.
T. A. Egerton and F. J. Stone, J.C.S. Furuday I, 1973, 69,22.
P. A. Jacobs, F. H. Van Cauwelaert, E. F. Vansant, and J. B. Uytterhoeven,J.C.S.
Faraday I , 1973,69,1056.
347
either 0-or 0;which is tightly associated with the alkali-metal cation, i.e.
a metal-deficient oxide or peroxide radical such as Na-0 or Na-0-0.
The 1 7 0 hyperfine structure of the e.p.r. spectra of the superoxide ion formed
on decationated HY zeolite has confirmed that the two oxygen atoms are
the 1 7 0 1 7 0 - pattern was thus consistent with the peroxy-type
structure. The surface-to-ion bond shows from 95 to 100% ionic character,
which is considerably different from organic peroxy-radicals. A complementary e.s.r. study of the oxygen species adsorbed on y-irradiated zeolites
HY and HZ has identified the species with peroxy-radicals weakly bonded to
oxygen atoms of the zeolite lattice (35). The proposed reaction mechanism
(3 5 )
corresponds to the coupling of one of the twounpairedelectronsof themolecular oxygen with the unpaired electron of the V-centre, which is created by
the ?-irradiation, according to the scheme shown.
Several physicochemical investigations of the nature of the hydroxy-groups
present on the surface of zeolites have been ~ n d e r t a k e n . ~In
~ ~an- attempt
~~~
to clarify the interpretation of the i.r. spectra of OH groups present on zeolite
surfaces, Jacobs and U y t t e r h o e ~ e n have
~ ~ ~recorded
a ~ ~ ~ the i.r. spectra of both
X- and Y-type zeolites in the OH stretching region under high resolution.
The spectra have been measured as a function of both A1 and H content787
and the pretreatment conditions.788The spectra have been broken down into
six different components; an assignment is proposed which considers the four
different types of oxygen ions as possible sites for proton location. The i.r.
spectra of water molecules adsorbed by X-type zeolites (LiNaX, NaX,
KNaX, and CsNaX) have been recorded in an effort to determine the different
states of water molecules in the zeolite cages.789At low adsorption coverage
the water molecules were found to interact mainly with the zeolite cations;
the spectra show that one OH group of an adsorbed water molecule is bound
to the oxygen of the zeolite skeleton and the other is free. In the case of
CsNaX zeolite, where adsorption is weaker, both hydroxy-groups of the
adsorbed water molecules interact, presumably with the oxygens of the
zeolite lattice. The results of an i.r. and d.t.g. analysis of the dehydration of
decationized Y-type zeolites have shown that there are different forms of
adsorbed water, which differ in the strength of the bonding with the surface;790it was also observed that the introduction of cations into the zeolites
enhanced the retention of water molecules. The Russian authors790claim that
the results of these experiments and those of further experiments to investigate
catalytic activity cast doubt on the hypothesis that structural -OH groups
348

are the sole source of catalytically active centres on decationized zeolites. An
analysis of the adsorption of water by zeolite NaY has been carried out as a
function of the aluminium content of the zeolite.791The volume of the micropores has been found to depend on both the aluminium content and the
pretreatment temperature, whereas the adsorption energies of the sites vary
regularly with the aluminium content and depend only on the overall density
of the negative charges associated with the aluminium.
Removal of H 20 molecules and NHf cations from and the formation of
OH groups on NH:-exchanged erionite on gradual heating from room
temperature to 700 OC has been observed in an i.r.-spectroscopic
Interaction of the OH groups with propylene and ammonia has been examined
to determine their accessibility and reactivity; the results of the propylene
absorption can be interpreted in terms of two different OH groups, one of
which is more inaccessible than the other. An i.r. study of the interaction of
deuteriotoluenes with the structural OH groups of decationized zeolites has
been carried
It is concluded from the results that these zeolites have
two types of centres, differing in the nature of the adsorption of the toluene.
The first type consists of structural OH groups which interact with adsorbate
molecules via formation of a weak hydrogen bond with the w-electron system
of the ring. The second type of centre consists of co-ordinatively unsaturated
metal atoms which form electron-acceptor bonds with the aromatic ring.
The adsorption of both water and ammonia molecules on copper(r1)exchanged Y-type zeolites has been studied in an attempt to elucidate the
structures of the co-ordination spheres of these molecules in zeolite CuY.794*795
The results of a U.V. spectroscopic and gravimetric investigation794have
established that three types of stable structures can exist in a CuY zeolite
containing ammonia. Prior to evacuation at 70 O C , the spectra of the zeolite
suggest that the Cu2+ion forms a complex with five ammonia molecules that
is located in the large cavities of the zeolite. The first thermally stable coordination structure, which exists between 70 and 110 OC, is formed by two
ammonia molecules together with oxygen ions of the zeolite framework.
Evacuation at 200 OC yields the second type of co-ordination sphere, in which
only one ammonia molecule remains. The third type of structure is formed
after evacuation at 3OO0C and corresponds to complete loss of ammonia
from the co-ordination sphere with entry of the Cu2+ ions into the zeolite
framework. In a complementary gravimetric study of the adsorption and
desorption of ammonia on CuY zeolite795the large ammonia uptake (relative
to that of Nay, Cay, and decationated Y-type zeolite) was attributed to the
formation of copper(I1) ammine complexes, which were thought to be mainly
in the form of [Cu(NH3),I2+, (cf. the previously described five-co-ordinate
complex).7g4The adsorption of ammonia was also found to cause the migration of Cu2+ions from the sodalite cages to the supercages; this was concluded
from both e.s.r. and CO absorption data.795
The nature of NO and NOz when adsorbed on CrI'I- and Nirl-exchanged
X- and Z-type zeolites has been studied using e.s.r. and i.r. spectroscopy.796
349
Adsorption of NO on Crl'*-exchanged zeolite samples, subsequentlyreduced
to CrII by either hydrogen or carbon monoxide, has been shown to give rise
to a d5 Cr+NOS complex; under certain conditions a diamagnetic complex
(36) was also formed. Adsorption of NO2 gave rise to the similar d6complex
(36)
Cr+NO+. Similarly, NO and NOz adsorb on Nil'-exchanged zeolites to form

d9 complexes Ni+NO+ and Ni+NO$. It was concluded that NO adsorption
could be used as a rough but easy means of locating the exchanged cations
and to show cation migration from hidden sites towards accessible ones.796
The adsorption of NO and NOz on Y-type zeolites has also been studied as
part of a wider investigation of the ionization and electron-transfer reactions
in such zeolites.797When Y-type zeolites are exposed to sodium vapour and
subsequently to oxygen, Nai+ centres, effectively an electron trapped in a
cage shared among four Na+ cations, and 0;radicals are formed. Copper(I1)and nickel(I1)-exchangedY-type zeolites were also found to undergo electrontransfer reactions with adsorbed NO and NO2 gases. Thus the reactions
considered in this study were:
+
+
+
Na -+ Na+
eNaO, + Na+
0,
NaCl 3 Na+
C1NO + Cu+(or Ni+)
NO+
Cu*+(orNP+)
Cu+(or Ni+)
NOa 3 Cu2+(orNi2+) NO,
+
+
+
+
As written, most of these reactions are endothermic processes. Yet each one
has been found to proceed with amazing facility within the zeolite crystal.
The most notable feature common to all reactions is that they result in an
increase in the number of ions within the zeolite cages. It is suggested that a
proper arrangement of these additional charged species within the periodically situated void spaces should result in an increase of the crystalline Madelung energy; it is thought that it is this gain in the crystalline energy which
offsets the endothermicity of these reactions.797
The adsorption of CO on cation-exchanged (Zn2+, Mn2+, Co2+, Ni2+,
Cu2+, Ba2+, U02+, and Ce3+) Y-type zeolites has been i n v e ~ t i g a t e d The
.~~~
bivalent ions all produced sites for specific CO adsorption even at low degrees
of exchange. Thus, unlike Ca2+, these ions do not have a total preference for
internal sites in the prisms or sodalite units that are inaccessible to CO. Very
little CO was specificallyadsorbed onto CeY even at high degrees of exchange;
this confirms that Ce3+ions favour internal sites. 1.r.-spectroscopic studies of
CO, adsorbed on cation-exchanged (Ca2+ and Mg2+) Y-type zeolites799
Inorganic Chemistry af the Main-group EIements

have been used to determine the distribution of Ca2+and Mg2+ions over the
cation sites, since the physisorption of CO, provides a sensitive method for
the detection of these cations in supercage positions. It was found that the
cation distribution over different exchange sites is not the same in hydrated
and dehydrated samples. High-temperature outgassing of the samples facilitates migration of the bivalent ions from positions in the supercage to small
cavity positions (preferentiallysite I); bivalent ions in the dehydrated samples
are present in the supercage only when the degree of ion exchange is 4 6 4 8 %
or higher. For high-temperature chemisorption of CO, the chemisorbed
species are closely related to co-ordinated CO2- anions.799
350
Gerrnaniurn(1v) Oxide and Germanates. Germanium(1v) oxide reacts with

anthranilic acid to form triclinic Ge(C7H7O2N),Cl30H,which on heating
exhibitedendothermic effects owing to its decomposition at 185 and 245 'C.Soo
At 1213-1364 K, GeO, sublimes by the reaction:
The calculated enthalpy of sublimation is 134 kcal mol-1.801 The behaviour of
chlorine and sulphur impurities during the thermal treatment of GeO, in
oxidizing and reducing atmospheres has been studied. In air, chlorine impurities are completely removed from GeO, only at >900 "C. In freshly prepared
GeO,, the chlorine present is bound rather strongly, and its content starts
to decrease only at 4OO0C, but after two weeks it starts to be removed at
100 'C. Sulphur remains present in GeO, in significant quantities even after
2 h at 100 'C. In a hydrogen atmosphere, both chlorine and sulphur can be
removed from GeO, at 600 'C.*02
The crystal structure of Dy,.,,(GeO,),O consists of seven-fold and ninefold co-ordination polyhedra at dysprosium, and GeO, tetrahedra, r(Ge0) = 1.76-1.81 A.803The structure of K,Ge,017 shows similarity, in the
connection of polyhedra, with the feldspar structure. Out of 32 Ge atoms
in the unit cell, 24 are surrounded tetrahedrally by oxygen atoms at
an average distance of 1.75 A, and the remainder are pentaco-ordinate. The
oxygen environment of these atoms can be considered as a distorted trigonal
bipyramid, being joined by sharing edges. The Ge-0 bond distances in the
GeO, polyhedra range from 1.77 to 1.97A8i.so4D.t.a. and X-ray diffraction
showed that MgGeO, and Mg,Ge04 are formed simultaneously from MgO
and GeO, at 990-1250 "C. The addition of 2 % V,O, markedly increased
the rates of reaction at 1000-1200 'C; addition of MnO, was less effective
E. K. Maiorga, R. IS. Gridasova, B. E. Zaitsev, and A. 1. Ezhov, Zzoest. V.U.Z.,
801
Khim. i khim. Tekhnol., 1973, 16,297 (Chem. Abs., 1973,79,73 038j).

E. K. Kazenas, D. M. Chizhikov, Yu. V. Tsvetkov, and Yu. V. Vasyuta, Zhur.fiz.
Khim., 1973,47,695.
I. S. Pashchenko, G. I. Petrov, V. V. Krapukhin, and L. N. Shigina, Izvest. Akad.
Nauk S.S.S.R., Neorg. Materialy, 1973, 9, 151.
E. L. Belokoneva, T. L. Petrova, M. A. Simonov, and N. V. Belov, Soviet Phys.
Cryst., 1972, 17,429.
E. Fay, H. Nollenkle, and A. Wittman, Z. Krist., 1973, 138,439.
EZernents of Group IV
351
at 1100 'C,while addition of TiO, and Fe203did not promote reaction. With
all additives except TiO,, initiation of the formation of MgGeO, occurred at
lower temperatures and the formation of MgGeO, was suppressed.805
Chromium metagermanate, Cr,GeO,, is prepared by heating a stoicheiometric mixture of GeO, and Cr203at > 1100 "C. It is ferromagnetic, with a
NCel temperature of 97 K.'06 Monoclinic single crystals of M,Ge,O, (M = K,
Rb, or Cs) are obtained by heating mixtures of the oxides at a M:Ge ratio
of 8-4: 1 at 4 5 0 4 6 5 'C. The germanates are isotypic with K6Co,0, and
contain Ge,O, groups with four-co-ordinate germanium.807Thallium and
silver aluminogermanates, MAlG%O, (M = T1 or Ag), may be transformed
into the hollandite-typestructure by high-pressure treatrnent.'O8 Solid solutions
are formed when GeO, and SiO, are heated to 1300-1500C.809 In the
BaO-Ge02-H,O system at 25 "C, in addition to the known barium germanate
BaO,GeO,,SH,O, a new hydrate barium tetragermanate Ba0,4Ge02,4H20
has been observed.810The X-ray diffraction patterns, derivatograms, and i.r.
spectra of crystals of Na,0,Ge0,,7H20, and of its dehydration products,
show that the compound has the formula Na2EGe(OH)6],4H20.s11The rareearth oxides M203 (M = La, Y , Tb, or Lu) react with GeO, in aqucous
ammonia at pH 10.2-10.3 in 1 : 1, 2:3, and 1 :2 ratios to give M,GeO,,
M2Ge207,and 2M,0,,3Ge0,.812
The phase diagram for the system Na,O-ZnO-Ge0,-H,O
shows the
formation of Zn,GeO,, Na,ZnGeO,, and Na,Ge,0,0.813 Hydrothermal
crystallization in the system CdO-GeO,-LiCl-H,O gives the cadmium and
lithium germanates Cd,GeO,, CdGe,O,, Li,GeO,, Li,Ge,O,, and Li,O, 10Cd0,12Ge02 as the chief phases.*14The crystal structures of rhombohedra1
Cd,(Ge0,)s15 and of monoclinic Cd2(Ge,06),816prepared from hydrothermal
crystallization in the KC1-Cd0-Ge0-OH, system, have been determined. The
latter consists of GeO, tetrahedra fused together, r(Ge-0) = 1.75,1.76,1.82,
1.84 A. The GeO, tetrahedra form 'pyroxene' chains (GeZO,), with two
tetrahedra in the repeating link.s16 Hydrothermal crystallization of the
L. N. Belonogova, V. N. Kryukov, and N. G. Vyazova, Zzuest. V.U.Z., Khim. i khim.
Tekhnol., 1973, 16,666 (Chem. Abs., 1973,79,61 103 p).
SO8 G. Odent and F. Annabi, Compt. rend., 1972, 275, C , 1275.
W. Schartau and R. Hoppe, Naturwiss., 1973, 60, 105.
N. Kinomura, J. Amer. Ceram. SOC.,1973, 56, 344.
G. M. Esirkegenav, A. M. Smagulova, and A. P. Bazhanov, Nauch. Tr., Kaz.Politekh.
1971,485 (Ckem. A h . , 1973, 78, 37 365j).
E. A. Knyazev, S. I. Smyshlyaev, and V. V. Berezkin, Russ. J. Inorg. Chem., 1972,
17, 1637.
E. A. Knyazev and A. N. Akulov, Russ. J. Znorg. Chem., 1973, 18, 139.
812 V. D. Kozlov, R. L. Magunov, and V. S. Krylov, Khim. Suoistva Soedin. Redkozemel.
Elem., Dokl. Vses. Soveshch. Fiz.-Khim. Prinzen. Redkozemel. Elem., Ikh Soedin.
Splauou, 6th, 1969, p. 57 (Chem. Abs., 1973, 79, 60 981m).
0. S. Tarasenkova and B. N. Litvin, Vestnik. Moskou. Univ., Geol., 1973, 28, 112.
814 L. N. Dem'yanets and N. V. Suvorova, Soviet PAYS. Cryst., 1973, 18, 133.
E. L. Belokoneva, Yu. A. Ivanov, M. A. Simonov, and N. V. Belov, Soviet Phys.,
Cryst., 1972, 17, 177.
A. N. Kornev, L. N. Dem'yanets, B. A. Maksimov, U. V. Ilyukhin, and N. V. Belov,
Soviet Phys. Cryst., 1972, 17, 244.
805
352
Na,O-CdO-GeO-H,O system has yielded eight phases : CdGe,O, (triclinic),
Cd,Ge04 (orthorhombic), C&Ge300 (triclinic) Na,Ge,O,,,, Cd,Ge,0,,9H20
(monoclinic), nCdO,mGeO,,pH,O ,GeO, ,and Cd0.817Phase equilibria in
the Ca,Ge04-BaGeO, system,818 the lead@) metagermanate-molybdateoxide ternary system,8l9the 2Ba0-2Ca0-GeO2-SiO2 quaternary reciprocal
system,820and the Ge02-Pb0-W03 system821have also been studied.
Cation distribution and local distortions of the crystal lattice have been
studied by Mossbauer spectroscopyin the series of garnets N3Fe2_2M,G%012
(N = Ca or Cd; M = Al,Ge, CrySr, or In).822The i.r. and Raman spectra of
pyrogermanates of the type A2Pb2Ge20, (A = K, Rb, or Cs) have been
recorded.823The partial enthalpies of liquid PbO and of tetragonal GeO, in
lead germanate melts have been measured calorimetrically at 900 C in the
range 0-65 mole % Ge02.824Dielectric measurements on powdered, crystallized, lithium germanates of composition Li2Ge205,Li,Ge03, Li4Ge04,
and Li,GeO, have been performed in the temperature range 20-800 0C.s25
Zn-Mn isomorphism in Na2ZnGeOc26and Zn,GeO:27 crystals has been
investigated by e.s.r. spectroscopy.
Tin(1v) Oxide and Stannates. The molecular species Sn02 and Sn,O,(D,,)
are the major reaction products when tin vapour is cocondensed at 20 K with
krypton or nitrogen matrices containing a few mole per cent of oxygen.
Small amounts of O,, SnO, Sn303,and other tin oxide species are also produced. Normal-co-ordinate analysis indicates that SnO, is linear (Dcob) with a
principal Sn-0 stretching constant of 5.36 mdyn A-1 in krypton matrices.
The use of unscrambled 1602-180,
isotope mixtures indicates that the SnO,
is formed by the direct insertion of a tin atom into an oxygen molecule, and
that the major route to Sn,O, appears to be the subsequent reaction of SnO,
system, Mossbauer spectroscopy
with a second tin atom.828In the Sn,,Sb,O,
shows that the oxidation states of the tin and antimony are IV and v, respectively. The conduction electrons resulting from Sb substitution are distributed
over the entire lattice. As the Sb content increases, the l%b isomer shift and
s-electron density at the tin nucleus also increase, as expected for a conduction
817
819
820
821
822
823
824
82L
826
8a7
N. G. Duderov, L. N. Demyanets, E. L. Belokoneva, A. N. Lobachev, and N. V.

Belov, Souiet Phys. Cryst., 1973, 17,916.
R. G. Grebenshchikov and V. I. Shitova, Doklady Akad. Nauk S.S.S.R., 1972,204,
466.
G. A. Bukhalova, V. T. Maltsev, and Z.N. Machavatiani, Rum. J . Inorg. Chem.
1973,18,264.
R. G. Grebenshchikov and V. I. Shitova, Russ. J. Inorg. Chem., 1972, 17, 1487.
A. G. Bergman, Z . N. Machavariani, and V. T. Maltsev, Russ.J. Inorg. Chem., 1972,
17, 1633.
I. S. Lyubutin, L. M. Belyaev, R. Grzhikhova,and I. Lipka, Souiet Phys. Cryst., 1972,
17, 116.
P. Tarte, M. J. Pottier, and A. M. Proces, Spectrochim. Acta, 1973, 29A, 1017.
F. Miiller and 0. J. Kleppa, 2.anorg. Chem., 1973,397, 171.
H. Bittner and H. Hiebl, Monatsh., 1973, 104, 1383.
I. P. Kuzmina, A. N. Lobachev, V. M. Vinokurov, N. M. Nizamutdinov, and L. A.
Volkova, Souiet Phys. Cryst., 1973, 18, 110.
D. W. Feldman, J. Chem. Phys., 1973, 58, 363.
A. Bos and J. S. Ogden, J. Phys. Chem., 1973,77, 1513.
353
bandcomposed largely of Sn 5s orbitals.829The rare-earth stannates M,(Sn03)3
(M = La, Pr, Nd, Sm, Eu, Gd, Dy, or Y)are prepared by the reaction of
MCl, and Na,Sn03 in water. On heating to 700-900 OC, they are converted
into the corresponding pyrostannates M2Sn20,, which can also be prepared
by the reaction of M203in HCl with SnCl, in aqueous ammonia at 900 0C.s30
The behaviour of the colouring ion CJ? in the systems BeO-Sn0,-Cr,O,,
MgO-SnO,-Cr,O,, Ca0-Sn02-Cr203, and Sn02-Cr203has been investigated.
Neither the formation of solid solutions nor compounds could be detected
in the BeO-SnO, system; Mg,SnO, was formed in the MgO-SnO, system at
temperatures > 1500 0C.s31The solid solution Fe,,Sn,O,
is limited to x =
0.58 whatever the heat treatment. Fe,SnO, is metastable if it exists. The tin is
always located at the octahedral sites.832The co-operative Jahn-Teller effect
in the ZnMn,O,-Zn,SnO,
system has been studied.s33 Colloidal particles
from hydrous tin oxide colloids have been deposited on hydrophobic surfaces,
rendering them hydrophilic.834
Lead(1v)Oxide and Plumbates. Annealing of a-PbO, at 46-80

"C produces
as intermediates a-PbO, and p-PbO, and finally PbO and Pb304.835Under
hydrothermal conditions at 150-300 OC, a-PbO, is transformed into P-PbO,.
At 360-380 O C and 280400 kg ern-,, B-PbO2 is converted selectively into
Pb203 with water or aqueous NaOH or KOH solution (<0.1 moll-I> and
into Pbl,Ol, at concentrations > 1 moll-l. Pb,O, has a stoicheiometric
composition and produces a-PbO, by acid treatment (HNO, or HClO,).
Pb1z019 is non-stoicheiometric. PbO, (x = 1.42-1.58) is not affected by acid
treatment.s36
Colourless to pale yellow Na6Pb04has an ordered Na,O structure in which,
according to the formulation as [O"Na,Na"] [O'(PbOz),], there are 'isolated'
Pb& groups connected to each other by Na' and Na".837The similar pale
yellow Na6Pb05 contains isolated PbO, groups of pseudo-tetragonal pyra m i d ~ . The
* ~ ~lead atoms in Cs,PbO, are also five-co-ordinated by oxygen
atoms in tetragonal-pyramidal environments, the structure containing
$ [PbO,,,O,] chains.839Ba0,Pb02,H20may be prepared by the addition of
BaCl, to a solution of PbO, in NaOH solution, or by autoclaving an aqueous
T. Birchall, R. J. Bouchard, and R. D. Shannon, Canad. J. Chem., 1973, 51, 2077.
G. G. Mel'chenko and V. V. Serebrennikov, Zhur. neorg. Khim., 1973,18, 1172.
831 L. Tcheichvili, Bol. SOC.Espan. Ceram. Vidrio, 1972, 11, 75 (Chem. Abs., 1973, 78,
11 065m).
832 C. Djega-Mariadassou, F. Basile, P. Poix, and A. Michel, Ann. Chim. (France),
1973,8,15.
833 M. Nogues and P. Poix, Ann. Chim. (France), 1972, 7, 301.
834 J. T. Kenney, W. P. Townsend, and J. A. Emerson, J. Colloid Interface Sci.,1973,42,
589.
835 M. L. Galantseva and E. M. Shamba, Gertsenorsk. Chteniyn, Fiz.Poluproo. Elektron.
Kratkoc Soderzh, Dokl., 25th, 1972, 44 (Chem. Abs., 1973,79, 60 936a).
836 E. Torikai, Y. Kawami, and H. Maeda, Osaka Kogyo Gijritsu Shikensho Kiho, 1972,
23,218 (Chem. Abs., 1973,79, 38 069y).
837 P. Panek and R. Hoppe, 2. anorg. Chem., 1973,400,229.
838 P. Panek and R. Hoppe, 2. anorg. Chem., 1973,400,208.
P. Panek and R. Hoppe, 2.anorg. Chem., 1972,393,13.
82g
830
354
suspension of BaO and PbO, at 170-210 "C. CaO,PbO2,4H,O was prepared

using concentrated NaOH, and on heating lost 75 % water at 210 O C and the
remainder at 3 8 0 4 0 O C . Using the autoclave method, Ca0,Pb0,,3H20
was obtained.840CdO reacts hydrothermally with PbO, in 1 :2 and 2: 1 molar
ratios at 262 "C and 50 atm to give CdPb,O, and Cd2Pb0,, respectively.841
RhzO, reacts with PbO at 580--600C with the formation of the semiconducting compound PbRh,O,. Reaction with Pb@g and Pb02 in the range
of their stability (up to 550 "C and 420 "C,respectively) was not observed.842
Magnetic measurements on single crystals of PbMn,O, show a transition to a
weak ferromagnetic state at 63 K.843The compound [Pb6O(OH),](C10,),,H2O
crystallizes in two modifications. The structure of the p-form contains discrete [Pb,O(OH)t+] groups. The six lead atoms occupy the corners of three
distorted tetrahedra connected by common faces. The central tetrahedron
contains an oxygen atom at its centre. The outer tetrahedra have one
hydroxide oxygen outside each of their six unshared faces.844
Molecular Oxides. The eight-membered siloxane ring in 2,6-cis-diphenylhexamethylcyclotetrasiloxane has a 'boat' form (Figure 11). The average
Si-0
and Si-C
bond distances are 1.631 and 1.851 A, respectively. The
Figure 11 Structure of 2,6-cis-diphenyZhexamethyZcyclotetrasiloxane

(Reproduced by permission from Acta Cheni. Scand., 1973,27, 1203)
N. F. Fedorov and S. A. Zagarova, Izvest. V.U.Z.,Khim. i khim. Tekhnol., 1973,16,
13~0
841
795 (Chem. Abs., 1973,79,60 980k).

N. F. Fedorov and S. A. Zagorov, Izvest. Akad. Nauk S.S.S.R., Neorg. Materialy
1973,9,872.
842
843
I. S . Shaplygin and V. B. Lazarev, Russ. J . Inorg. Chem., 1973, 18,275.

B. I. Al'shin, R. V. Zorin, L. A. Drobyshev, and S. V. Stepanishchev, Soviet Phys.
Cryst., 1972, 17,489.
A. Olin and R. Sonderquist, Acfa Chem. Scand., 1972,26,3505.
355
angles at the silicon atoms are all close to the tetrahedral value, and the mean
Si-0-Si
bond angle is lM.2.845Cyclotrisiloxanes have been made by the
heterofunctional condensation of 1,3-disiloxane diols with dichlorodiorganosilanes in a solvent in the presence of an arnir~e.*~~
Up to 94 % of lowmolecular-weight cyclic products (72-84 % of tetrasiloxanes) are obtained
in the hydrolytic condensation of Me2SiC1, and MePhSiCl, in ether.847
Andrianov et al. have prepared spiro-siloxanes by the heterofunction condensation method as illustrated in Schemes 20,848
21,848and 22.849Some of
Scheme 20
Scheme 21
HO-S1
Sic14
-+
2
HO-Si
P2
\
/"
R2
Scheme 22
the products exist as cis- and trans-stereoisomers. Tri-imidodisiloxane is

formed by the ammoniolysis of Si,OCl, at -78C. The thermal decomposition, which starts at 15OoC, is accompanied by a set of deaminations
The relative
which lead to amorphous silicon oxynitride, Si,ON,, at 600 0C.850
845
846
847
848
D. CarIstrom and G. Falkenberg, Acta Cheirr. Scartd., 1973, 27, 1203.

Yu. A. Yuzhelevskii, T. V. Kurlova, E. G. Kagan, and M. V. Suvorova, J. Gen.
Chem. (U.S.S.R.), 1972, 42,2006.
A. G. Kuznetsova, S.A. Golubtsov, N. P. Telegina, V. I. Ivanov, and G. G. Pchelintseva, J. Gen. Chem. (U.S.S.R.), 1973, 43, 300.
K. A. Andrianov, A. B. Zachernyuk, B. D. Lavrukhin, and N. G. Vasilenko, Dokludy
Akad. Nauk S.S.S.R., 1972,204,498.
K. A. Andrianov, A. B. Zachernyuk, and B. D. Lavrukhin, Doklady Akad. Nuuk
S.S.S.R.,1972,207,876.
850
24
P. Goursat, D. Giraud, and M. Billy, Bull. SOC.chim.France, 1972, 3681.
356
basicities of a number of di- and cyclo-siloxaneshave been investigated by the
i.r. method.851
The liquid-phase reaction between hexamethyldisiloxane and TiCl, at
25 OC has been studied by lH n.m.r. The three equilibrium constants K , for
the successive replacement of chlorine atoms by OSiM,e groups:
TiC14--(n--l)(OSiMe3)n--l Me3SiOSiMe3
& TiC1,-,(OSiMe3), + RCI
decrease with increasing n: Kl > lo5; K , = 8; and K , = 0.11.852Tris(trimethylsilyloxy)vanadium(v) imines are obtained by the reaction of
NH4V03with silylamines:853
NH4VO3
+ 2HN(SiMe&
NH4V03
-2NH3,
+ 3PrHNSiMe3 -iE:ip)
(Me3Si0)3V=N-SiMe3
(Me3SiO)3V=N-Pr
The reaction of anhydrous copper(1) chloride with NaSiOMe, in THF yields

tetrameric (CuOSiMe,),, for which the cage structure (37) is suggested.
,SiMe3
Me3Si,
~ F u - 0
0-cu
**..*o-t/cu
To\
Me&
SiMe3
(37)
Other heterosiloxane derivatives of Cu, Ag, and Au are formed from the
phosphine complexes (PR,),MCl (M = Cu or Ag; R = Me; n = 1, 2, or 3 :
M = Au; R = Me or Ph; n = 1):
(PR,),MCl
+ NaOSiMe3
(PR3),MOSiMes
+ NaCl
The arsine complex (Ph,As)AuOSiMe, was similarly prepared. The tris(phosphine)-copper and -silver complexes and the gold complexes are
monomeric, with two-co-ordinate metal; the mono- and bis-(phosphine)copper and -silver siloxanes are oligomers (38) and (39), with bridging
SiMe3
Me3P.gJ
0I
\Ag.4--PMe3
Of
SiMes
(38)
851
852
853
SiMe3
Me3p\
\o, 1
/Me3
Merpp\o/A<
PMes
I
SiMea
(39)
S. N. Borisov, N. P. Timofeeva, Yu. A. Yuzhelevskii, E. G. Kagan, and W. V. Kozlova, J . Gen. Chem. (U.S.S.R.),
1972, 42, 863.
V. V. Yastrebov, Russ. J . Inorg. Chem., 1972, 46, 1664.
F. Becker, J . Organometallic Chem,, 1973, 51, C9.
3 57
silanolate groups between metals having co-ordination numbers 3 and 4.854
Organozinc siloxanes (40) are obtained by the protolysis of the Zn-C bond.
The compounds are dimeric, and react with alcohols to form siloxyzinc
alkoxides (41), and with water to give R$iOH, RIH, and Zn(OH),. Reaction
RiZn
+ RIH
RgSiOH
R,R2 = Etor Ph
RiSiOZnR
(40)
.OH1
RjSiOZnOR3
(41)
with molecular oxygen produces peroxyzinc compounds. Unstable (tri-
chloromethyl)(triphenylsiloxy)zinc, which decomposes to Ph,SiOZnCl and

dichlorocarbene, is formed with chloroform or carbon tetrachloride. Thermal
decomposition of Ph,SiOZnR (R = Et or Ph) results in the transfer of phenyl
groups from silicon to zinc, followed by further radical decomposition of the
resulting diorganozinc compounds.855The thermal decomposition of silyloxycadmium compounds is similar, but with Ph,SiOAIEt, only exchange of
phenyl and ethyl groups between the metals takes place, with the Si-0-A1
bridge remaining intact.856 The pentafluoro-orthotellurates Me,MOTeF,
(M = Si, Ge, or Sn) and Si(OTeF,), have been synthesized by the reaction of
Me,Sn, Me,MCl, and SiC1, with HOTeF, or AgTeF,. The tin compound
Me,SnOTeF, forms a five-co-ordinate complex Me,Sn(L)OTeF, with
acetonitrile, but DMSO causes ionization to give [Me3SnL2]S[F,Te0]-.857
The crystal structure of (Ph,Ge),O consists of discrete molecules (Figure
12). The Ge-0-Ge
bond angle is 137, somewhat higher than in (H,Ge),O
(126.5). The Ge-0 and Ge-C bond distances are 1.75A and 1.97A,
respectively.858Bis(trialky1tin)oxides form 1 :1 and 1 :2 adducts with SnCl,
andTiCl,, and 1 :1 complexeswith SbC1,.859Compounds containing Sn-0-B
linkages are readily obtained by the azeotropic removal of water from
mixtures of bis(tributy1tin) oxide with boric acid, with or without added
glycol. , uiz.860
2B(OH)3
854
855
856
857
858
859
860
+ 3(B~~Sn)~0
~ ( B u ~ S ~ O ) ~3BH 2 0
H. Schmidbaur, J. Adlkofer, and A. Shiotani, Chem. Ber., 1972, 105, 3389.

G. G. Petukhov, R. F. Galiullina, Yu. N. Krasnov, and A. D. Chernova, J. Gen.
Chem. (U.S.S.R.),
1972,42, 1037.
V. N. Pankratova, L. P. Stepovik, I. V. Lomakova, and L. A. Pogodina, J. Gen.
Chem. (U.S.S.R.),1972,42,1740.
F. Sladky and H. Kropshofer, J.C.S. Chem. Comm., 1973, 600.
L. G. Kuzmina and Yu. T. Struchkov, J. Struct. Chem., 1972,13, 884.
R. C. Paul, V. K. Mahajan, S. C. Ahluwalia, R. K. Sharma, and S. P. Narula, Znorg.
Nuclear Chem. Letters, 1973, 9, 893.
S. K. Mehrotra, G. Srivastava, and R. C. Mehrotra, J. Organometallic Chem., 1973,
47,39.
Inorganic Chemistry of the Main-grorcp Elements
358
28
Figure 12 Structure of (Ph,Ge),O

(Reproduced from J. Struct. Chem., 1972, 13, 884, by permission of the
Consultants Bureau)
The polarographic behaviour of Ph,PbOH and Ph,Pb(OAc), has been
investigated in aqueous alcoholic media.8s1
Alkoxides. The hydrolysis of tetraethoxysilanehas been studied under various
solvent and temperature conditions. The structures of the resulting polymers

are dependent upon the reaction conditions employed, those formed at high
temperatures being highly condensed
The vibrational spectra of
Si(OR)4 (R = Me or Et)863and the vapour pressure of Si(OEt)ca4have been
measured. The reaction of Si(OMe), with SbF, yields the mixed fluoromethoxysilanes Si(OMeXF, Si(OMe),F,, Si(OMe)F,, and SiF,. Phosphorus
pentachloride replaces the methoxy-groups of Si(OMe,)F by chlorine to form
C1,SiF.865Alkoxy-iodine(v) tetrafluorides, IF,OR, and Me,SiF are formed
from the reactions between IF, and Me,SiOR.866The intermolecular exchange
and configurational stability of organotin alkoxides and phenoxides have
been studied by n.m.r. techniques. For triorganotin alkoxides, exchange of
884
J. P. Colliard and M. Devaud, Bull. SOC.chim..France,1972,4068.

B. W. Peace, K. G. Mayhan, and J. F. Montle, Polymer, 1973, 14,420.
J. W. Ypenburg and H. Gerding, Rec. Trav. chim., 1972,91,1245.
N. N. Dyachkova, E. N. Vigdorovich, and L. A. Ivanyutin, Rum. J . Inorg. Chem.,
865
V. G. Noskov, L. N. Kalinina, and M. A. Englin, J. Gen. Chem. (U.S.S.R.), 1972,
863
1973,47,258.
42,2025.
868
G. Oates and J. M. Winfield, Inorg. Nuclear Chem. Letters, 1972,8, 1093.
359
Figure 13 Structure ofBu,Sn[O,(CH,),]

(Reproduced by permission from J. Organometallic Chem., 1973,55, C19)
alkoxide groups is much faster than inversion.867Polymeric diorganotin

alkoxides [-R',Sn-O-R2-O-],
have been prepared from RiSnCI, and
NaO-R2-ONa.868 The preliminary results of an X-ray investigation of
dibutylstanna-2,6-dioxacyclohexanehave been reported. The crystal consists
of monomeric Bu2Sn(0,C,H,) units which are connected together by intermoIecular 0 -+ Sn co-ordination, forming chains (Figure 13). The tin atom
possesses tetragonal pyramidal geometry, the four oxygen atoms being in a
867
868
U. Folli, D. Iarossi, and F. Taddei, J.C.S. Perkin 11, 1973, 1284.

C. E. Carraher and G. A. Scherubel, Makromol. Chem., 1972, 160,259.
360

plane [r(Sn-0) = 2.05 A; r(Sn * * * 0)= 2.57 A] and the two butyl groups
perpendic~lar.~~~
In bis(pentane-2,4-dionato)dimethyltin(rv), Me,Sn(C,H,O,),,
the two
methyl groups and two bidentate pentane-2,4-dionate residues complete
nearly perfect co-ordination at tin. (Figure 14). The Sn-C and Sn-0 bond
Figure 14 Bond distances around the tin atom in Me2Sn(02C5H,)a

distances are 2.14 A and 2.18,2.20 A, re~pectively.8~~

The molecular structure
of this compound in solution has also been investigated by Tobias using
Raman spectroscopy.871The reactions of B u S ~ O and
~ , ~BuSn(OPri), with
glycols yield derivatives of the types (42) and (43).872Nearly neutral aqueous
'
ro,v
Bu
/ O B
~ O ~ s n - o S n '01
Bu
Ptesn/O?X
hJ
= (CH,),,(CH,),, or CH2CHMe
(42)
(43)
solutions of catechol react at room temperature with amorphous magnesium

trisilicate to form crystals of Mg[Si(~at),],9H,O.~~~
l-(Chloromethy1)- and 1-(3-chloropropyl)-silatrane are synthesized by
transalcoholysis of the corresponding (chloroa1kyl)triethoxysilanes with
87O
J. Pommier, E. Mendes, J. Valade, and J. Housty, J. Organometallic Chem., 1973,

55, (219.
G. A. Miller and E. 0. Schlemper, Inorg. Chem., 1973,12,677.
V. B. Ramos and R. S. Tobias, Spectrochim. A d a , 1973, 29A, 953.
D. P. Gaur, G. Srivastava, and R. C. Mehrotra, J . Organometallic Chem., 1973, 47,
95.
D. W. Barnum, J. M. Kelley, and B. Poocharoen, Inorg. Chem., 1973,12,497.
361
2,2,2-triethanolamine in the presence of KOH as a catalyst.s74Similarly,
though without a catalyst, the stannylalkanolamines Bu,SnORINRi,
Bu,SnOR1NR2SnBu3 (R1 = CH,, CH,CH,, or CH,CHMe; R2 = H, Me, or
Et) can be obtained from Bu3SnOEt and the appropriate alkan0larnine.8~~
The crystal structure of l-(a-naphthy1)germatrane is shown in Figure 15.
UI)
C(2)
Figure 15 Projection of l-(u-naphthy1)germatrane molecule onto the equatorial

plane of the bipyramid
(Reproduced from J. Struct. Chern., by permission of the Consultants
Bureau)
The co-ordination polyhedron of the germanium atom is a distorted trigonal
bipyramid with a short Ge-N interaction (2.24 A). The Ge-C and Ge-0
bond distances are 1.94 and 1.77 A, respectively.87sThe l H n.m.r. spectra of
alkyltin stannatranes at various temperatures show that two processes of
intramolecular motion take place. A Berry pseudo-rotation (AG,*,= 18.3
kcal mol-l) and a ring inversion (AG& = 14.1 kcal mol-l) between four
different conformations are proposed.877 In the complex Sn [(OC,H,),NC,H,OH],, the tin atom is octahedrally co-ordinated by four oxygen and
two nitrogen atoms of the triethanolamine molecules. The co-ordination
polyhedron at the tin atom is shown in Figure 16. The Sn-N bond
distances are rather long (2.332,2.383 A), and the mean Sn-0 bond distance
is 2.038 A?78A band at 557-600 cm-l in the i.r. spectra is attributed to the
Si + N bond in organosilatrane~?~~
874
M. G. Voronkov, V. M. Dyakov, and V. P. Baryshok, J . Gen. Chem. (U.S.S.R.),
876
1973,43,445.
D. P. Gaur, G. Srivastava, and R. C. Mehrotra, 2.anorg. Chem., 1973,398,72.
876
877
878
819
A. A. Kemme, Ya. Ya. Bleidelis, R. P. Shibaeva, and L. A. Atovmyan, J . Struct.

Chem., 1973,14,90.
A. Zschunke, A. Tzschach, and K. Ponicke, J . Organometallic Chem., 1973,51, 197.
H. Follner, Monatsh., 1972,103, 1438.
E. E. Shes,takov, M. G. Voronkov, V. 0. Reikhsfeld, and G. I. Zelchan, J. Gen.
Chem. (U.S.S.R.),
1973, 43, 306.
362
Figure 16 Co-ordinationpoZyhedron at tin in Sn[(OC,H,),NC,H,OH],

(Reproduced by permission from Monatsh., 1972,103,1438)
C~r6oxyZutes.The reactions of the potassium salts of aromatic thio-acids

K+-SC(O)Ar with Me,SiCl give the corresponding thionoacyloxysilanes (a),
whilst with Me,MCl (M = Ge or Sn) the corresponding thiol esters (45)
ArCOSiMes
(44)
0.
II
MesSiC1
4
11
ArCS-
K+
Me3MCl
Gc or Sn)
11
ArCSMMcs
(45)
are formed.880Zuckerman has investigated in detail the factors controlling

the solid-state structures adopted by trialkyltin derivatives of amino-acids
and dipeptides. The controlling factor appears to be the steric effect of the
groups at tin and the a-carbon substituent in the ligand. When both are
small, a one-dimensional co-ordination polymer formed by bridging aminogroups is the preferred structure; in intermediate cases carboxylate group
co-ordination, utilizing equatorial or equatorial-axial positions, presumably
through chelation in monomeric units, becomes preferred; when both are
large, only simple, four-co-ordinate monomers are found.8810882Massspectral studies show that dimethylchlorotin carboxylates are polymeric,
whereas tetramethyl-l,3-bis(carboxy)distannoxanes and tetramethyl-l-(carboxy)-3-hydroxydistannoxanes are d i m e r i ~The
. ~ ~synthesis
~
and structure of
organotin mercaptocarboxylates have been investigated by Stapfer and Herber. The compounds are readily prepared from the mercapto-acid and the
880
881
882
883
S. Kato, W. Akada, M. Mizuta, and Y. Ishii, Bull. Chem. SOC.Japan, 1973,46,244.

B. Y. K. H o and J. J. Zuckerman, Znorg. Nuclear Chem. Letters, 1973, 9, 849.
B. Y. K. Ho and J. J. Zuckerman, Znorg. Chem., 1973,12, 1552.
C. S. C. Wang and J. M. Shreeve, J. Organometallic Chem., 1973,49,417.
363
appropriate organotin oxide. Monoalkyltin oxides form 1:2 adducts (46)
in which one of the ligands retains a free -SH group. With dialkyltin oxides,
the resultant 1 :1 adducts (47) are linear polymers. Two different organotin
mercaptocarboxylates are formed with bis(trialky1tin) oxides; a dinuclear
monomer (48), in which one metal atom is chelated by both oxygen atoms of
RSn03/2 + 2HSCH2C02H
R3SnOSnR3
+ HS(CH2),C02H
+ H20
[BuSn(02CCH2SH)(02CCHzs>ln
(46)
R3Sn
*/
0
C(CH2),$SnR,
the carboxy-group while the other tin atom is bonded through the sulphur of
the thiol group, and a polymeric compound (49) containing both bridging
carboxylate ligands and free thiol groups.884The thermal decomposition
of BaSn(C204)2,0.5H20and Ba2Sn(C,04),,6H,0 in air or oxygen proceeds
through an intermediate mixture of BaCO, and SnO,. In uacuo, tin reduction
and re-oxidation occurs during decomposition. The final products of
decomposition of the two oxalates are BaSnO, and Ba,Sn04, re~pectively.~~~
The plumbylation of lead tetra-acetate to form aryl-lead tricarboxylates
has been investigated, and high-yield routes have been devised.886--s88U.V.
photolysis of lead(1v) fluoroalkanoates (RCO,),Pb at 77 K leads initially to
the formation of fluoroalkyl radicals.889The reactions of lead tetra-acetate
with HCl, HBr, or oxine, acetylacetone, or benzoylacetone in THF lead to the
885
88e
889
C. H. Stapfer and R. H. Herber, J . Organometallic Chem., 1973, 56, 175.

P. K. Gallagher and F. Schrey, Therm. Anal., Proc. Int. Conf., 3rd, 1971 (Chem. Abs.,
1973,78,131 560r).
D. De Vos, J. Spierenburg, and J. Wolters, Rec. Trav. chim., 1972, 91, 1465.
D. De Vos, F. E. H. Boschman, J. Wolters, and A. Van der Gen, Rec. Trau. chim.,
1973,92,467.
D. De Vos, J. Wolters, and A. Van der Gen, Rec. Trau. chim., 1973,92,704.
P. B. Ayscough, J. Machova, and K. Mach, J.C.S. Furaduy I , 1973, 69,750.
364
formation of mixed Pb(OAc),X, compounds.sg0The formation of the sevenco-ordinate compound Me,Pb(OBz),HMPA (OBz = benzoate; HMPA =
hexamethylphosphoramide) in solution has been demonstrated by lH
n,m.r.891The polarographic behaviour of PhPb(OAc),, in aqueous alcohol
has been examined.892
Oxyacid Deriuatiues. Both Mironovsg3and Tarbellsg4have investigated the
synthesis of silyl carbonates. The routes shown in Scheme 23 gave high
yields of the desired products,
2RsSiOH
+ COC12 + 2Et3N
RsSiONa
+ C02
R;SiOH
ii-iv
-+
R3SiOCOOSiR3 -I-2NEt,HCt
R3SiOCOONa
i
I_+
R3SiOCOOSiRs
+ NaCl
R:SiSCOOSiR%,
R,SiOCOONa
+ COClz
-+
R3SiOCOOSiRs
Reagents: i, RSSiCI;ii, NaH; iii, COa; iv, QSiC.1
Scheme 23
In dimethyltin dinitrate the two nitrate groups are almost coplanar and
are bonded to the tin in an unsymmetrically bidentate manner. The two
methyl groups and the tin atom are not collinear (LCSnC = 144"), and the
geometry at tin is intermediate between tetrahedral and octahedral. The
Sn-C bond distances are approximately equal (2.11, 2.12~4);two of the
Sn-0 bonds areshort (2.17,2.15 &andtwoaremuchlonger (2.42,2.70
Diaryl-lead dinitrates Ar2Pb(N03)2are easily obtained by precipitation with
nitric acid from solutions of the corresponding diacetates in acetic acid.
Prepared in this way the compounds contain water of crystallization; anhydrous compounds may be obtained by thermal dehydration.8Q6
The reaction
of the dinitrates Ar,Pb(NO,),,nH,O (n = 0 or 2; R = Ph,p-Tol, rn-Tol, or
3,5-Me2C,H,) with concentrated sulphuric acid causes autonitration, producing bis(nitroary1)leadsulphates, which may be transformed into plumboxanes,
and then into bis(nitroary1)lead diacetates. The 3-nitro-derivatives are
890
891
89a
893
894
895
896
M. S. A. El-Meligy and F. Huber, 2.anorg. Chem., 1973,399,349.

M. Aritomi, Y. Kawasaki, and R. Okawara, Inorg. Nuclear Chem. Letters, 1972, 8 ,
1053.
J. P. Colliard and M. Devaud, Bull. SOC.chim. France, 1973, 1541.
V. F. Mironov, V. D. Sheludyakov, and G. D. Khatuntsev, J . Gen. Chem. (U.S.S.R.),
1972,42,2114.
Y . Yamamoto, D. S. Tarbell,J. R. Fehlner, and B. M. Pope, J . Org. Chern., 1973,38,
2521.
J. Hilton, E. K. Nunn, and S. C. Wallwork, J.C.S. Dalton, 1973, 173.
E. Kunze and F. Huber, J . Organometallic Chem., 1973,51,203.
365
obtained when the rneta-positions are unsubstituted; in the case of Ar = mtolyl and 3,5-Me,C,H3, the 2-nitro-derivatives are obtainedFg7
The complex silicophosphates Sr4M,(SiO)4(P04)202(M = La, Nd, Y, or
Er) have been prepared by calcination at 1200-1350C of mixtures of
(NH4),HP04, SrCO,, ethyl silicate, and the rare-earth sesquioxides. They
possess apatite structures.8BsThe structure of Ge(OH)PO, is built up of
octahedral chains of composition [GeO,(OH)], which are connected by PO,
tetrahedra forming a three-dimensional network, which exhibits one-dimensional disorder phenomena. The Ge-0 bond distances range from 1.84 to
1.90A, mean 1.8581.899 The crystal structure of Ge,O(PO,), consists of
isolated [GeO,] octahedra and [Ge20,] double tetrahedra linked by PO,
tetrahedra forming a three-dimensional network. Average Ge-0 bond
distances are: 1.863 A (octahedral) and 1.704 81 (tetrahedra1).90 The solid
solutions Cal,Pb,(PO,),(OH),
( x = 0-10) have been prepared by coprecipitation in a C0,-free atmosphere at 37 OC by the simultaneous addition
of stoicheiometric amounts of aqueous NH,H,PO, and a solution containing
the desired proportions of Ca2f and Pb2+ to an aqueous ethylenediamine
Lead and tin tetra-acetates form H,[M(HSO,),] (M = Sn or Pb) in disulphuric acid, which behave as weak acids of the system. Tin tetraethoxide,
Ph4Sn, and Ph,SnCI are solvolysed to afford Sn(HSO,), in all three cases.
Tetra-alkylstannanes form the corresponding trialkyltin cations, as do tri- and
di-alkyltin chlorides. Solvolysis also occurs with Bu,SnCI, (Bu,Sn),O, and
Pr,SnO, but (Pr,Sn),O forms the tripropyltin cation.902 The hexakis(fluorosulphato)stannate(rv) ion has been synthesized in two ways
M = K,Cs,orNO
Methyl fluorosulphonate reacts with tetramethyltin, forming trimethyltin

f l u o r ~ s u l p h a t e .Two
~ ~ ~ general synthetic routes to methyltin chlorofluorosulphates and trifluoromethanesulphonates of the general type Me,SnCl,(so3x)4-n-m (n, rn = 0, 1, or 2; X = F or CF,) have been described:
solvolysis of the corresponding methyltin chlorides in the appropriate
*08
Oo0
Ool
Oos
Oo4
E. Kunze and F. Huber, J. Organometallic Chem., 1973, 51,215.

N. F. Fedorov, I. F. Andreev, and Sh. Yu. Azimov, Russ. J. Inorg. Chem., 1972,17,
1537.
H.Mayer and H. Vollenkle, ZJKrist., 1972,136,387.
H.Mayer and H. Vollenkle, Monatsh., 1972,103,1560.
S. V. C. Rao and N. S. Chickerur,J.Inst. Chem., Calcutta, 1972,44,177(Chem. Abs.
1973,79,48 771k).
R. C. Paul, J. K. Puri, and K. C. Malhotra, J . Znorg. Nuclear Chern., 1973,35,403.
P. A. Yeates, J. R. Sams, and F. Aubke, Znorg. Chem., 1973, 12,328.
C.Eaborn, N. Farrell, J. L. Murphy, and A. Pidcock, J . Organometallic Chem., 1973,
55, C68.
366
A
Figure 17 Structure of Me,Sn02SCH2C=CH

(Reprc3duced by permission from Acta Cryst., 1973, B29, 560)
sulphonic acids, and ligand-redistribu t ion reactions between methylt in

chlorides and s u l p h o n a t e ~ Trimethylgermanium
.~~~
methylsulphinate Me,Ge02SMe is obtained by the reaction of Me,GeBr with Ag0,SMe in
acetone.906 The presence of 2,2-bipyridyl facilitates the SO2 insertion
into tetramethyl- and tetraethyl-tin, yielding the corresponding bis(sulphinates) R2Sn(0,SR)2 at -30 O C , via the initial formation of
the monosulphinate R,Sn02SR.907 When the reaction with liquid
P. A. Yeats, J. R. Sams, and F. Aubke, Inorg. Chem., 1972,11,2634.
E. Lindner and K. Schardt, J . Organometallic Chem., 1973,50, C33.
E. Lindner and D. W. R. Frembs, J . Organometallic Chem., 1973,49,425.
367
SOz is carried out at 6OoC, disproportionation of sulphur takes
place, resulting in the formation of the corresponding bis(trialky1tin)sulphates (R,Sn),SO, and alkanethiosulphonic acid S-esters RS02SR.908The
crystal structure of the product of SOz insertion into Me,SnCH,CCH has
been determined (Figure 17). Me,SnO,SCH,C=CH is polymeric with planar
trimethyltin groups [r(Sn-C) = 2.161 A] and bridging sulphinate groups
[r(Sn-0) = 2.301 81].909
Germanium dioxide aquate and alkali-metal nitrates react with iodic acid to
yield alkali-metal hexaiodatogermanates(Iv), M2[Ge(I03),] (M = NH,, K ,
Rb, or Cs). The compounds M1[MIV(IO,),] (MI = NH,, K, Rb, or Cs;
MIv = Ge, Sn, or Pb) are i s o m o r p h o ~ s . ~ ~ ~
MisceZZaneous Deriuafiues. The treatment of 0-silyl-hydroxylamines

RiSiONH, with R$Wl and triethylamine at 25 OC affords a mixture of the
isomers R,SiONHSiR: and R:SiONHSiR;, whereas when the reaction is
carried out at 0 'C, only the former is formed. Both products isomerize at
120 OC, the favoured isomer being that which is less hindered at oxygen.g11
The dis-symmetric compounds R1,SiONHSiRg may also be obtained by the
reaction of RiSiONH, with Ph,C=C=NSiR:,
there being no rearrangement .912 The 0-substitu ted hydroxylamine derivatives MqSnONEt
R,SnONHCOPh (R = Pr or Ph), R,SnOPhCOPh (R = Me, Pr, or Ph),
Me,SiONPhCOPh, and Ph,PbONPhCOPh have been synthesized from the
hydroxylamine and Me3SiCl or organo-tin or -lead oxide. All appear to be
monomeric except Me3SnONRCOPh (R = H or Ph), which appear to be
loose dimers in the solid. In the tin and lead compounds, the carbonyl group
is intramolecularly co-ordinated to the metal atom.913
The silicon(1v)-Schiff base derivatives Si(OAc),(L) and SiL, [H,L = oHOC,H,C(Me) :NXOH and 2-HOCIoH,CH :NXOH, x = -(CHz),-,
-CMe,CH,-,
or -CHEtCH,-]
are obtained by the reaction of Si(OAc),
with the bifunctional terdentate Schiff base. The derivatives are monomeric in
boiling benzene, indicating five- and six-co-ordinate silicon, r e ~ p e c t i v e l y . ~ ~ ~ ~ ~ ~
The GeIV-Schiff-base compounds Ge(sap)2, Ph,Ge(sap), and Ph,Ge(sen)
[sapH, = N-(2-hydroxyphenyl)salicylaldimine; senHz = NN '-ethylenebis(salicylaldimine)] have been prepared from the germanium chloride and the
sodium salt of the Schiff base.916In NN'-ethylenebis(salicy1ideneiminato)dimethyltin(1v) the quadridentate salen ligand occupies the four equatorial
,,
U. Kunze, E. Lindner, and J. Koola, J. Organometallic Chem., 1973, 55, 267.

P. D. Ginderow and M. Huber, Acta Crust., 1973, B29, 560.
R. Frydrych, F. Schellhaas, and C. Pflugmacher, Z . anorg. Chem., 1973,399, 73.
F. Duboudin, E. Frainnet, G. Vincon, and F. Dabesat, Compt. rend, 1973, 276, C,
1469.
s12 J. P. Llonch, F. Duboudin, G. Vincon, F. Dabescat, and E. Frainnet, J . Organometallic Chem., 1973, 52, C24.
913 P. G. Harrison, Inorg. Chem., 1973, 12, 1545.
R. N. Prasad and J. P. Tandon, Synth. Inorg. Metal-Org. Chem., 1973, 3 , 157.
sls R. N. Prasad and J. P. Tandon, Indian J . Chem., 1973, 11, 366.
s16 F. Maggio, T. Pizzino, V. Romano, and A. Giovenco, Inorg. Nuclear Chem. Letters,
1973,9,639.
368
t"
369
positions of a distorted octahedron around the tin atom, the methyl groups
being mutually trans (Figure 18). The bond lengths in the two crystallographically independent molecules are in the ranges : r(Sn-0) = 2.19-2.25
A; r(Sn-N) = 2.24-2.27 A; r(Sn-C) = 2.07-2.16 A.917The five-coordinate dimethyltin complex (50) is solvated in strongly co-ordinating solvents such as DMSO and HMPA, becoming six-co-~rdinate.~~~
Silicon, Germanium, Tin, and Lead Derivatives of Sulphur, Selenium, and

Tellurium.-Thio-germanates, -stannates, and -plumbates, and Related Systems.
The equilibrium phase diagram of the quasi-binary system Cu2S-GeS2shows
the existence of two definite compounds Cu,GeS, and Cu,GeS,. Cu,GeS, has
a monoclinic superstructure of a deformed zinc-blende type. Cu8GeS, has
a phase change at 55 C, with an enthalpy of transformation of 1.7 kcal
mol-l. The low-temperature a-form is monoclinic, while the high-temperature
p-form is face-centred cubic.919The Ge-Te-S ternary system contains GeTeGeS, and TeGeS, quasi-binary sections.920The structure of monoclinic
La,GeSS is made up of two kinds of sheets parallel to the xOz plane: alternately, sheets of (GeS,), tetrahedra and (LaS),,. Ge-S bond distances
range from 2.17 to 2.25
The compounds Na4M2S2,14H,0 (M = Ge or
Sn) are isotypic, and contain dimeric isolated M2S:- ions consisting of two
tetrahedra sharing a common edge. The terminal M-S bonds are significantly
shorter (Ge: 2.170A; Sn: 2.332A) than the bridge bonds (Ge: 2.272A;
Sn: 2.450 A) in the strained four-membered rings.922A study of the SnS2-Na2S
system has given rise to four crystallinephases :Na,SnS,, Na,SnS,, Na,Sn,S,,
and Na4SnSs.923Na,SnS4 is made up of discrete [SnS,]- tetrahedra which
M. Calligaris, G . Nardin, and L.Randaccio, J.C.S. Dalton, 1972, 2003.
K. Kawakami and T. Tanaka, J. Organometallic Chem., 1973, 49, 409.
M. Khanafer, J. Rivet, and J. Flahaut, Bull. SOC.chim. France, 1973, 859.
920 S. Maneglier-Lacordaire, J. Rivet, P. Khodadad, and J. Flahut, Bull. SOC.chim.
France, 1973, 1930.
921A. Mazurier and J. Etienne, Acta Cryst., 1973, B29, 817.
B. Krebs, S. Pohl, and W. Schiwy, 2.anorg. Chem., 1972,393,241.
F. V. G. Daniel and J. C. Dumas, Compt. rend., 1973, 275, C, 741.
918
919
370

show only minor distortions from regularity. The Sn-S bond distance is
2.388 A?24The structure of BaSnS, is a distortion of the NaCl structure, and
can be considered as a composite of the Bas and SnS stru~tures.~,5
Na,Sn,S,
contains isolated Sn2$- ions consisting of two tetrahedra joined by a common
corner.926In Pb,SeBr, all lead atoms have trigonal-prismatic co-ordination,
additional neighbours above the prism faces raising the co-ordination number
to 7, 8, or 9. In Pb,S,I, some of the lead atoms are surrounded by 61 1s
or 51 3 s in the same extended trigonal-prismatic arrangement; others are
in the centres of the PbI, octahedra. Pb7S2BrIois isostructural with Th,S,,,
with a statistical occupancy of part of the metal and non-metal positions.927
PtGeSe crystallizes in the orthorhombic cobaltite structure, an ordered
variant of the pyrite structure. PtGeS and PtSiSe are i s o t y p i ~The
. ~ ~synthesis
~
of GeS, from the elements takes place in two stages: GeSe is first formed and
then reacts with more Se to form GeSe2.929The GeSe,-Cu,Se system is very
similar to the analogous sulphur system,Q19and contains the two compounds
Cu2GeSe3and CU8GeSe6. The former is a monoclinic superstructure of a
deformed blende type. Cu,GeSe, has a phase transition at 55 'C. The hightemperature form has a hexagonal structure and the low-temperature form is
a superstructure of the former. The phase-transition enthalpy is 1.076 cal
Phase equilibria in the ternary systems Pb-Ga-Seg31 and Au-PbTeQ3,have also been investigated.
Molecular Compounds containing M-S, -Se, and -Te (M = Si, Ge, Sn, or
Pb) Bonds. The reaction of SiS, with 2,6-dimethylphenol produces (2,6Me,C,H,O),SiSH and [(2,6-Me,C6H,0),SiS]~.Q~
SiS, with 2,6-dirnethylphenol and ethanol gives the mixed ethoxyphenoxysilanes (EtO),Si(OC6H3Me,),,
(n = 1-3).934 Ethyl-lithium reacts with the compounds Et,MEH
(M = Si or Ge; E = S, Se, or Te) to give the corresponding lithium salts.935
Hexamethyldisilthianereacts with (CF,),PCl to give (51), which reacts with
HBr to give (CF,),SH and Me,SiBr, and with further (CF,),PCl to yield
(CF3)zPCl
MesSiSSiMe,
(CF3)2PSSiMe3
Me3SiCI
(51)
J. C. Dumas, F. V. G. Daniel, and E. Philippot, Cryst. Struct. Comm., 1973, 2, 157.
J. E. Iglesias and H. Steinfink, Acta Crysr., 1973, B29, 1480.
926 B. Krebs and W. Schiny, Z . anorg. Chem., 1973,398, 63.
9 a 7 B. Krebs, Z . anorg. Chem., 1973,396, 137.
g 2 8 P. Entner and E. Parthe, Acfa Cryst., 1973, B29, 1557.
seQ R. A. Beskrovnaya, L. D. Dyatlova, and V. V. Serebrennikov, Tr. Tomsk. Univ.,
1971,403 (Chern. A h . , 1973,78, 131 485).
s30 C. Carcaly, N. Chezeau, J. Rivet, and J. Flahaut, Bull. SOC.chim. France, 1973, 1191.
s31 R. Eholie and J. Flahaut, Bull. SOC.chim. France, 1972, 1191.
s32 B. Legendre and C. Souleau, Bull. Soc. chim. France, 1972,472.
s33 W. Wojnowski and W. Wojnowska, Z . anorg. Chem., 1973,397,69.
s34 W. Wojnowski and W. Rodziewicz, 2.anorg. Chem., 1973,396, 108.
Q36 A. I. Charov, M. H. Bochkarev, and N. S. Vyazankin, Zhur. obshchei Khim., 1973,
43,772.
924
Eleinents of Group IV
37 1
(CF3),PSP(CF3), and Me,SiC1.936 Conformational isomerism in cyclotrisilthianes has been studied by lH n.m.r.937~938
Tetra(methy1germanium) hexasulphide has been shown by X-ray crystallography to possess an adamantanetype structure (Figure 19). The mean Ge-C and Ge-S bond distances are
1.922 A and 2.218 A, respectively.939Vibrational spectra for organotin
thiolates and s u l p h i d e ~ and
~ ~ ~for~ ~
the* ~compounds M(SR), (M = Si, Ge,
or Sn)932have been reported.
Figure 19 Structure of(MeGe),S6

Reactions between disodium dicyanoethylene-1,2-dithiolate (Na,mnt)
and diorgano-tin and -lead dihalides in the presence of R,N+, Ph4P+, and
Ph,As+ ions lead to the formation of ionic complexes of the types [Ph,E]
[M(mnt)R,X] (E = P or As; M = Sn, R = Me, X = C1, Br, or I; R = Ph,
X = Cl; M = Pb, R = Ph, X = C1) and [R,N][M(mnt),R?j] (M =.Sn,
R1 = Me or Ph; M = Pb, R1 = Ph). The co-ordination number of the tin in
these complexes is five or six, depending on the cation employed. Neutral
complexes [R,M(mnt)] (M = Sn, R = Me or Ph; M = Pb, R = Ph) may
also be obtained.s43 The trimethylmetal dithiocarboxylates Me,MS2CR
(M = Si, Ge, or Sn) have been prepared by treatment of MqMCl with
Og8
D37
D38
D3D
040
041
D43
043
25
K. Gosling and J. L. Miller, Inorg. Nuclear Chenz. Letters, 1973, 9, 355.

M. M. Millard and L. J. Pazdernik, J. Organometallic Chem., 1973, 51, 135.
M. M. Millard, L. J. Pazdernik, W. F. Haddon, and R. E. Lundin, J. Organometullic
Chem., 1973,52,283.
R. H. Benno and C. J. Fritchie, J.C.S. Dalton, 1973, 543.
P. G. Harrison and S. R. Stobart, J. Organometullic Chem., 1973, 47, 89.
G. Davidovics, G. Mille, M. Delmas, and J. Chouteau,J . Mol. Structure, 1973,16,59.
J. Y. Ypenburg and H. Gerding, Rec. Trau. chim., 1972,91, 111.
E. S. Bretschneider and C. W. Allen, Znorg. Chem., 1973, 12,623.
372

amine salts of the dithiocarboxylic acid.g44The Mossbauer spectra of organotin(1v) dithiocarbamates indicate that the dithiocarbamate ligand functions
as an anisobidentate moiety, forming one strong and one weak bonding
interaction in some compounds.g45Trimethyltin mono- and di-thiocarbamates, ureas, and thioureas react with transition-metal carbonyl compounds,
forming the corresponding transition-metal derivatives.946Bis(trimethy1germyl, -stannyl, and -plumbyl) sulphides, selenides, and tellurides react with
chromium, molybdenum, and tungsten hexacarbonyls to displace carbon
monoxide to form the complexes (Me,M),E -+ M(C05) (M = Ge, Sn, or
Pb; E = S, Se, or Te; M = Cr, Mo, or W).047-g49 Methylseleno-derivatives
of silicon, germanium, and tin, Me,-,M(SeMe),
(M = Si, Ge, or Sn;
n = 1 4 ) , have been prepared by several routes: the reaction of MeSeH
with the organometallic amine, and the reaction of the metal halide with
MeSeLi, MeSeMgI, LiAl(SeMe),, and Me,SiSeMe.950 The organotin benzeneselenolates R,SnSePh (R = Bu or Ph) and R,Sn(SePh), (R = Me, Et, or
Bu) have been obtained from the organotin oxide or chloride and PhSeH.951
The NN-dialkylselenocarbamate complexes Me,Sn(SeCONR,),, Me,ClSnSeCONR,, and Me,SnSeCONR, may be prepared from Me,SnCl, or Me3SnC1
and the amine salt of the selenocarbamate. The carbonyl group in the
dimethyltin compounds is weakly co-ordinated to the tin atom, whereas
that of the trimethyltin derivative is free.952
Compounds containing Silicon-, Germanium-, Tin-, and Lead-Nitrogen

Bonds.-Molecular nitrogen is reductively silylated by Me,SiCl and lithium
metal in the presence of a transition-metal catalyst to give tris(trimethy1sily1)amine [reaction (101)].953Variable-temperature lH n.m.r. spectra for a
number of compounds containing Si-N bonds in which potentially diastereo6Me3SiC1
+ 6Li + NZ- m
2(Me&N
6LiCI
(101)
topic methyl groups are attached to nitrogen show that the rotational barriers
about Si-N bonds are lower than those about P-N or S-N bonds in
analogous systems.954Wannagat has prepared compounds, e.g. (52), containing the PTI1Si,N,O ring system by the standard route. The reactions of (52)
S. Kato, M. Mizuta, and Y. Ishii, J. Organometallic Chem., 1973, 55, 121.
J. L. K. F. de Vries and R. H. Herber, Inorg. Chem., 1972,11,2458.
Q46 E. W. Abel and M. 0. Dunster, J.C.S. Dalton, 1973, 98.
Q47 H. Schumann, 0. Stelzer, R. Weis, R. Mohtachemi, and R. Fischer, Chem. Ber.,
1973, 106,48.
Q4* H. Schumann, R. Mohtachemi, H. J. Kroth, and U. Frank, Chem. Ber., 1973, 106
1555.
Q49 H. Schumann, R. Mohtachemi, H. J. Kroth, and U. Frank, Chem. Ber., 1973, 106,
2049.
Q 5 0 J. W. Anderson, G . K. Barker, J. E. Drake, and M. Rodger, J.C.S. Dalton, 1973,1716.
Q51 E. C. Macmullin and M. E. Peach, J. Organometallic Chem., 1973, 52, 355.
Q62 K. Tanaka, S. Araki, and T. Tanaka, Bull. Chem. SOC.Japan, 1973, 46,2136.
Q53 K. Shiina, J. Amer. Chem. SOC.,1972, 94, 9266.
Q64 S. Chan, S. Distefano, F. Fong, H. Goldwhite, P. Gysegem, and E. Mazzola, Inorg.
Chem., 1973, 12,51.
g44
g45
Ekments of Group IV
373
~e~Si/qSiMe~
RPC*2
MeNH HNMe
2 ~ t , ~
-2Et,N,HCI
Me&
MeN,
0
SiMe2
,NMe
P
R
(52)
= MeorPh
to afford compounds containing the [PvSi,N,O]+ and PVSi,N,O ring systems

are contained in Scheme 24.955 Phosphoryl fluoride, POF,, reacts with
Me2Si
0
SiMe2
MeN,f,,NMe
C-S-
0
~ e ~ ~ ~i i ~ e ~
II
0
Me2Si/ %Me2
MeN,$,NMe
RMe
1-
MeN,+,NMe
P
R,\
Me&
SiMez
MeN,p,NMe
ii
R,
MeN/ P,NMe
Me2%, ,SiMe2
0
MeN,,,NMe
C N2
R/\~N--Sih4e3
Reagents: i, CS2;ii, 2 mol, Co12;iii, MerSiNs;iv, ise;v, Me1
Scheme 24
(Me,Si),N or LiN(SiMe3), in a 1 : l molar ratio to afford (Me,Si),POF,,

which with P203F4yields Me&N(POF&. The latter compound is also
available by the reaction of (Me,Si),N with P203F4in a 1 :2 molar ratio.
Phosphoryl chloride reacts with (Me,Si),N to afford an inseparable mixture
of (Me,Si),N and Me,SiO-PCI,=N-SiMe,.
A pure sample of this compound can be obtained by the reaction of OPCI, with LiN(SiMe3)2.956NMethyl(sily1amino)- and N-methyl(stanny1amino)-boranes, containing the
956
966
U. Wannagat, K. P. Giesen, and H. H. Falius, Monatsh., 1973, 104, 1444.

G. Czieslik, G. Flaskerud, R. Hofer, and 0. Glemser, Chem. Ber., 1973, 106, 399.
374

M-N-B
(M = Si or Sn) linkages, are obtained from the reaction of the
organometal chloride with N-lithioaminoboranes. In contrast to MGSnNMeBPh,, the compound Me,SnNEtBMe, is thermally unstable, decomposing
primarily into Me,B, (MeB-NEt),, and (Me,Sn),NEt.957 Organo-silicon,
-germanium, and -tin aminoboranes have also been prepared from the
halogenoborane and the lithium salt of the organometallic amine, and by the
cleavage of the M-N bond by halogenoboranes, e.g.:958
Me&NHGeMe,
A Me3CNLiGeMe3 ClPhBNMeZ*
(Me3Sn)3N + Me2NBRCl
Me3SnCl
/Me3
Me3GeN,
+ (M~SS~)~NBRNM~~
R = PhorNMez
The bis(trimethylsily1)amino-group has been used as a ligand to a variety

of metals stabilizing low co-ordination numbers. (Me,Si),NH reacts with
Grignard reagents forming the complex species (53), which also react with
(Me3Si)2NH
+ RMgX
[(Me3Si)2N]2MgMgX2,nEt20
(53) X = CI,Br,orI;n = 2 o r 4
(Me,Si) 2NLi
(Me3Si)2NH + Et2Mg
Et20+
[(Me3Si)2N]2MgYOEt2
(54)
110 C
[C Me3W2NI2M g
(Me3Si)2NLi forming (54), also obtained by the reaction of (Me&),NH
with diethylmagnesium. (54) loses the molecule of ether of solvation when
heated to 110 0C?59The monomeric complexes (55) have been prepared by
MC13
3LiN(SiMe3)2
M[N(SiMe3)2]3
(55)
3LiCI
M = La, Ce, PryNd, Sm, Eu, Gd, Ho,

Yb, Lu, or Y
057
958
969
I. Geisler and H. Noth, Chem. Ber., 1973,106, 1943.

R. L. Wells and R. H. Neilson, Synth. Znorg. Metal-Org. Chem., 1973, 3 , 137.
U. Wannagat, H. Autzen, H. Kuckertz, and H. J. Wismar, Z . anorg. Chem., 1972,
394, 254.
375
W
Figure 20 Structure of[(Me,Si),N],M, M = Sc or Eu
(Reproduced from J.C.S. Chem. Comm., 1973,669)
the reaction shown.g60X-Ray structural analyses of trishexamethylsilylamido-scandium(In),961-europium(rIr),961 and - i r o n ( ~ n )have

~ ~ ~ confirmed
their monomeric character and the presence of three-co-ordination at the
central metal. The scandium and europium compounds have a pyramidal
configuration [N-M-N
bond angles are 115.5' (Sc) and 116.6' (Eu)
(Figure ZO)], whereas the FeN, group in the iron compound is planar. In
addition, the FeNSiz groups are also planar, forming an angle of 49.2'
with the FeNa plane. The Si-C bond distances in all three compounds all
fall in the range 1.87-1.89 A; the Si-N bond lengths are 1.68 A (Eu) and
1.73 A (Sc and Fe), suggesting some degree of ionic bonding in the europium
compound. Electronic spectra, magnetism, and e.s.r. studies in M "(SiMe,),],
~~#~~*
(M = Sc, Ti, V, Cr, or Fe) compounds have been r e p ~ r t e d . ~The
reaction of LiN(SiMe,), with MCl,(PPh,), (M = Co or Ni) yields the threeco-ordinate complexes Co ~(SiMe,),],(PPh,) and Ni [N(SiMe,),](PPh,),.
The structures of the two compounds are shown in Figures 21 and 22, and
confirm the three-co-ordinate nature of the complexes. The Si-N bond
distances fall in the range 1.69-1.71 A?65
Salt-like compounds [R3NH]+[(C13Si),N]- are formed on the addition of
pyridine, or trimethyl- or triethyl-amine, to solutions of (Cl,Si),NH in
petroleum ether. The [Cl,Si),N]- ion shows the strongest Si-N bonds so far
known, with a bond order of two in accordance with the formulation
D. C. Bradley, J. S. Ghotra, and F. A. Hart, J.C.S. Dalton, 1973, 1021.
J. S. Ghotra, M. B. Hursthouse, and A. J. Welch, J.C.S. Chem. Comm.,1973, 669.
Q62 M. B. Hursthouse and P. F. Rodesiler, J.C.S. Dalton, 1972, 2100.
Q63 D. C. Bradley, R. G. Copperthwaite, S. A. Cotton, K. D. Sales, and J. F. Gibson,
J.C.S. Dalton, 1973, 191.
g64 E. C. Alyea, D. C. Bradley, R. G. Copperthwaite, and K. D. Sales, J.C.S. Dalton,
g60
Q61
1973, 185.
OS6
D. C . Bradley, M. B. Hursthouse, R. J. Smallwood, and A. J. Welch, J.C.S. Chem.

Comm., 1912, 8721.
376
Figure 21 Structure of Co[N(SiMe,),],(PPh,)

Figure 22 Structure of Ni[N(SiMe,),](PPh,),

377
+ -
IC13Si=N=SiC13].s66 Triorganophosphines, trialkyl phosphites, and dialkyl chlorophosphonites react with (Me3Si),NCl in ether at 0-10 O C to form
the N-silylphosphinimines (56).967 The trichlorophosphinimine (57) is obtain(Me3Si)sNCI
R3P -+
{(Me3Si)2N-PR3C1}
---+
Me3SiC1
+ Me3SiN=PR3
(56)
Pc15
+ LiN(SiMe&
-+
C13P=N-SiMe3
LiCl
Me3SiC1
(57)
ed by the reaction of LiN(SiMq), with PCl,.968 N.m.r. and i.r. studies on

15N-substituted bis(trimethylsi1yl)acetamide support the imide structure (58)
,SiMea
0
Me /%-SiMe3
I58)
(59)
rather than the amide isomer (59).s6gOligomeric cyclothiazasilanes (60) and

(61) have been prepared by the four different routes shown.970SS-DimethylR2
g66
D67
H. H. Moretto, P. Schmidt, and U. Wannagat, Z . anorg. Chem., 1972,394,125.

A. M. Pinchuk, M. G. Suleimanova, and L. P. Filonenko, J . Gen. Chem. (U.S.S.R.),
1972,42,2111.
D6*
D6D
970
E. Niecke and W. Bitter, Inorg. Nuclear Chem. Letters, 1973, 9 , 127.

C. H. Yoder and D. Bonelli, Inorg. Nuclear Chem. Letters, 1972, 8, 1027.
R. Appel and I. Rupert, Chem. Ber., 1973,106,902.
378
5Me2S(NH)2
S(HMeN)2SiR2 --+
//N-siMe3
+ 2ClzSiR2
2MezS
\N-
(60)
(60)
--+
(61)
Me3SiCl
%Me3
/N-siMe3
MezS
\N-SiMes
W)
2C12SiR2 --+ Me$
/N-siR2C1
- +
N-SiR2C1
R2SiCIz
sulphodi-imidealso forms 1 :1 complexeswith methyltin chlorides Me,SnCI,-,

(n = 0-3). With methyltin dialkylamines, transamination takes place
yielding NN'-bis (trimethy1)-SS-dimethylsulphodi-imide (62), and the polymeric stannanes (63) and (64).9'l Me,SnN: S(O)F,, prepared by the reaction of
Me
I
k=I--SnMez
Sn-(N=.?k
MeaSn-N=S=N-SnMe3
Me
(63)
(62)
(64)
NSF, with (Me,Sn),O in ether at -70 "C, decomposes at room temperature

to give Me,SnF and [N:S(O)F],,and it reacts with [F,(O)P],O to give
F,(O)PN :S(0)F2 and Me,SnOP(O)F,. It can also be synthesized from Me,SnCl and Hg [N :S(0)F,]2.972p-T~lyl~~lphodi-imide
reacts with Me3SnNMe2
to give (65), which reacts with further tin amine to yield (66).973
R-N=S=N-R
Me3SnNMe2
--+
Me3Sn-N-S=N-R
(65)
MesSnNMez
(Me3Sn-NR)zS(NMe~)
(66)
The reaction of Me,SnNMe2 with S4N4in a 1 :4 ratio produces (Me2N)$

and bis(trimethylstanny1)sulphodi-imide (67); this is cleaved by MqSiCl to
971
972
D. Hanssgen and R. Appel, Chem. Ber., 1972,105,3271.

R. Hoefer and 0. Glemser, 2. Naturforsch., 1972, 27b, 1106.
D. Hanssgen and W. Roelle, J. Organometallic Chem., 1973, 56, C14.
379
give the corresponding bis(trimethy1silyl)sulphodi-imide (68).973 S4N4 also
S4N4+ 4Me3SnNMe2
2(Me2N),S
2Me3Sn-N=S=N-SnMe3
reacts with (Me,Sn),N to form (67)and also the heterocycle (69), for which
the dimeric structure (70) is proposed.974(MqSn),NMe and (MqSn),N
S4N4
2(Me&n)aN
Me&
%' y
MelSn
+ 2Me3SnN=S=NSnMe3
\N=S
undergo Sn-N bond cleavage with a number of phosphorus- and sulphurhalogen derivatives to give (71)-(75). The compounds (71a) and (71b)
react with P203F4 to give (76).975
Bis(trifluoromethy1)methyleneamido-complexes of silicon, germanium,
and tin, Me,_,M[N:C(CF,),],
(M = Si, Ge, or Sn; n = 1 4 ) , have been
synthesized by substitution of the corresponding metal chloride.976The
stannyl-alkylideneamines Me,SnN: CR, (R = CF,, But, Ph, or p-MeC,H,)
undergo protolysis with HA (HA = H,O, ROH, PhC:CH, or C,F,H) to
give MqSnA, and they react with metal hydrides LMH to give, usually,
MqSn-ML complexes.Reactions with metal chloridesLMCl giveLM-N :CR,
complexes, and with unsaturated substrates (PhN=C==O or CH,=CHCN)
1 :1 insertion products are obtained.977
Ammoniolysis of GeCI, affords Ge(NH),, which is unstable at ambient
temperatures in the presence of NH4Cl and which forms the imide Ge,N3H.978
974
075
977
078
H. Roesky and H. Wiezer, Angew. Chem. Intertiat. Edrt., 1973, 12, 674.
H. W. Roesky and H. Wiezer, Chem. Ber., 1973, 106,280.
M. F. Lappert and D. E. Palmer, J.C.S. Dalton, 1973, 157.
M. F. Lappert, J. McMeeking, and D. E. Palmer, J.C.S. Dalton, 1973, 151.
M. Billy and M. Brossard, Compt. rend., 1973, 276, C, 859.
380
+ Me3Sn-N-P
II
Me3Sn-N-SnMe3
SiPFClz
fF2+ Me3SnF
(71)
Me
I/.\
(a) R = Me
(b) R = SnMe3
Me
MesSn--k-PHs
MeSSnF
Clz
(72)
Me
Me3Sn-N-SnMe3
CISOC4F9
R
I
Me3Sn-A-SOC4F9
Me or SnMe3
(Me&n)3N
Me3SnC1
(73)
FS02N:PC13 + (Me3Sn)eNPCl2=NSO2F
(75)
(71)
0
"
PaOsFh +F2P-N-P
R = MeorSnMes
F N
II
"7,
+ Me3SnOPFa
II
Fa
(76)
Me3SnCl
38 1
Treatment of R,Ge(NEt,), with amino-alcohols, amino-thiols thio-aci&s, or
dithiols result in the formation of the expected heterocyclic products.979
Organogermylamines react with phenylhydrazine to yield the corresponding
organogermylphenylhydrazines, which may also be obtained by substitution
using the lithium salt. Oxidation of R,GeNHNHPh with oxygen, lead
dioxide, or t-butyl peroxide leads to the formation of the di-imines
R,GeN=NPh.980
Tin-119m Mossbauer data for several classes of organotin-nitrogen bonded
compounds have been reported, including N-stannyl-amines, -imines,
Figure 23 Structure of stannic phthalocyanine

-amides, and -carbamates. Derivatives possessing the Sn-NR-C(0)X

group are intermolecularly associated via carbonyl-tin co-ordination, the
strength of the co-ordination varying with X in the manner H w OSnR, >
OR.g81 The reaction of alkyl iodides with 2-triorganostannyltetrazoles
results in the selective alkylation of the l - p o ~ i t i o nThe
. ~ ~tin
~ atom in stannic
phthalocyanine is eight-co-ordinate. The eight isoindole nitrogen atoms form
an antiprism (relative degree of rotation = 42') about the tin atom, with
Sn-N bond distances ranging from 2.32 to 2.37A (Figure 23).983X-Ray
photoelectron spectroscopy has been used to investigate the electronic
structures of some tin(1v) porphyrins and phthalocyaniiie~.~~~
978
G . Dousse, J. Satge, and M. Riviere-Baudet, Synth. Inorg. Metal-Org. Chem., 1973,
980
M. Riviere-Baudet and J. Satge, Bull. SOC.chim. Frame, 1973, 549.

P. G. Harrison and J. J. Zuckerman, J . Organometallic Chem., 1973, 55, 261.
T. Isida, T. Akiyama, K. Nabika, K. Sisido, and S. Kozima, Bull. Chem. SOC.Japan,
1973,46,2176.
W. E. Bennett, D. E. Broberg, and N. C. Baenziger, Inorg. Chem., 1973, 12, 930.
M. V. Zeller and R. G. Hayes, J. Amer. Chem. SOC.,
1973,95,3855.
3,ll.
981
982
g83
382
Inorgnnic Chemistry of the Main-group Elements
Phosphorus and Arsenic Derivatives of Silicon, Germanium, and Tin.-Me,SiCI
reacts with ButPC1,,
(n = 0-2) and magnesium in hexamethylphosphoramide to yield the silylphosphines (Me3Si),,PBut.
The analogous germanium and tin phosphines, and silicon, germanium, and tin arsines, are similarly prepared.985The organo-germanium and -tin phosphines and arsines
Me,MEHCF, (M = Ge or Sn; E = P or As) and (Me,M),ECF, are obtained
by treating Me3MPH, or (Me,M),P with H,ECF,. The reaction rates increased in the orders Ge < Sn, P < As, and Me,MPH, < (Me3M),P.gse~987
Tris(trimethyLgermy1 and -stannyl)phosphines react with (MeCN),M(CO),
(M = Cr or Mo) to give the complexes ([Me,M],P)3M(CO)3.988 Mixed
germanium-tin arsines are prepared by the reaction
Me,GeAsHR
+ Me,SnNMe,
R
-+ Me,GeAsRSnMe,
Me,Ge, Me, or Ph
+ Me,NH
The clathrates Ge,,A,X, (A = P, As, or Sb; X = C1, Br, or I) are synthesized in crystalline form either from the elements or from germanium and
suitable halides. At temperatures between 600 and 700 "C,they decompose to
the elements, halides, and other unidentified products. The cubic structure
consists of a three-dimensional E,, framework of tetrahedrally bound 38 Ge
and 8 A atoms; the 8 X atoms are situated inside the big cages of this
frame.990~991
Pseudohalide Derivatives of Silicon, Germanium, and Tin.-The
crystal
structure of triphenylsilyl azide is shown in Figure 24. The geometry at silicon
N(3)
Figure 24 Structure of Ph,SiN,

(Reproduced by permission from J. Inorg. Nuclear Chem., 1973,35, 1714)
Oa5
Og6
OS7
Oa8
OS9
Ooo
H. Schumann and L. Rosch, J. Organometallic Chem., 1973, 55,257.

S. Ansari and J. Grobe, 2. Naturforsch., 1972,27b, 1416.
S. Ansari, J. Grobe, and P. Schmid, J. Fluorine Chem., 1973, 2 , 281.
H. Schumann and W. W. DuMont, 1973,49, C25.
J. W. Anderson and J. E. Drake, J . Inorg. Nuclear Chem., 1973,35, 1032.
H. Menke and H. G . von Schering, Naturwiss., 1972, 59,420.
H. Menke and H. G. von Schering, 2.anorg. Chem., 1973,395,223.
383
is slightly distorted from tetrahedral; r(Si-C) = l.85A and r(Si-N) =
1.74 A. The SiN(l)N(2) bond angle is 120S0, indicating sp2 hybridization of
N(1). The N-N-N
group is linear (176.6).992Trimethylsilyl azide reacts
with BeCl,, MgX, (X = C1, Br, or I), BX, (X = F, Cl, or Br), and AlCl,
to form dimeric BeCI(N,),OEt,, polymeric Be(N3)z, polymeric MgX(N,),
trimeric BX,(N,), monomeric AICI,(N,), and polymeric AlCl(N,),, res p e c t i ~ e l yReactions
.~~~
with acid chlorides yield alkyl isocyanates :994
MesSiNs
+ RCR0
-+
RN=C=O
Me3SiC1 + Nz
Cl
With aldehydes and ketones, addition to the carbonyl group is observed,

yielding trialkylsilyloxycyano-alkanes (77).995 Treatment of Me,SiCI with
R1R2C=0
R3SiCN --+ R1R2C-O--SiR$
CN
(77)
AgCN gives MqSiCN, which contains 5.3% of the isocyanide MGSiNC

at 25 C. The microwave spectra of both have been recorded.996The silver
salt method has also been used to prepare organogermanium pseudohalides
MeH,GeX and MeGeX, (X = N,, CN, NCO, or NCS) and Ge(N,),,997
and organotin cyanides.998
The crystal structure of the terpyridyl complex of dimethyltin di-isothiocyanate shows that the tin is in pentagonal-bipyramidal co-ordination
(Figure 25). The two methyl groups occupy trans-axial positions [r(Sn-C) =
2.105 A]. The five equatorial positions are occupied by the three terpyridyl
and two NCS nitrogen atoms at distances of 2.515 8,and 2.283 A, respectively.
The equatorial plane is slightly distorted from planarity.999
Derivatives containing Silicon-, Germanium-, and Tin-Main-group Metal

Bonds.-Bonds to Group IVMetaZs. Dichlorocarbene (derived from PhHgCCI,
or PhHgCC1,Br) inserts into a Si-Cl bond of hexachlorodisilane, forming
C1,CSiCl2SiC1,. The reaction of Cl,SiSiCl, affords only a mixture of chloro(trich1oroacetoxy)disilanes. Methylene biradical, formed from Cu-catalysed
decomposition of diazomethane, reacts with Cl,SiSiCI, in ether between
992
E. J. Corey, V. Cody, M. D. Glick, and L. J. Radonovich, J. Inorg. Nuclear Chem.,

1973,35, 1714.
N. Wiberg, W. C. Joo, and K. H. Schmid, 2.anorg. Chem., 1972,394,197.

Q94 W. R. Peterson, J. Radell, and S. S. Washburne, J . Fluorine Chem., 1972, 2 . 437.
Q96 H . Neef and R. Miiller, J . prakt. Chem., 1973, 315, 367.
Q96 J. R. Durig, W. 0. George, Y . S . Li, and R. 0. Carter, J . Mol. Structure, 1973,16,47.
9 9 7 J. E. Drake and R. T. Hemmings, Canad. J . Chem., 1973,51,302.
QQ8 T. N. Srivastava, S. N . Bhattacharya, and K. K. Bajpai, J . Indian Chem. Soc., 1972,
993
49,1143.
99Q
D. V. Naik and W. R. Scheidt, Inorg. Chem., 1973, 12, 272.
384
Inorganic Chemistry of the Main-group Eienients
C(33)
(323)
Figure 25 Structure of Me,Sn(NCS),(terpy)

(Reproduced by permission from Inorg. Chew., 1973,12,272)
-40 and -3OOC to afford (78). Further reaction causes insertion into a
second Si-Cl bond.lM0When pentaphenylmethyldisilane is photolysed at
cu
C13SiSiC13 CH2Ne--N; (ClCH,)Cl,SiSiCI,

(7 8)
CH2Na
r
(ClCH2)CleSiSiCle(CH2C~)
-N2
2537 for 2 h at 55 OC in [hydro~y-~H]methanol

and cyclohexane, Ph,(CH,D)SiOMe and Ph,SiH are obtained in approximately 60% yield. These
products are consistent with a dehydrosilylation mechanism in which an
intermediate such as (79) (or its equivalent , e.g. the biradical Ph,Si-cH,)
must be important.lool
loooM. Weidenbruch and C. Pierrard, Angew. Chem. Internat. Edn., 1973, 12,500.
lool P. Boudjouk, J. R. Roberts, C. M. Golino, and L. H. Sommer, J. Amer. Chem. Soc.,
1972,94,7926.
385
E.p.r. and U.V. studies have been used to examine the formation of chargetransfer complexes between permethylpolysilanes and tetracyanoethylene.
It was concluded that the bonding pairs of electrons of the Si-Si bonds
donate electrons to tetracyan~ethylene.l~~~*~~~
The vibrational spectra of
rnethyl~hloro-~
and
~ ~ methylmethoxy-disilanes1005and of the trisilanes
Si,X, (X = C1, OMe, or Ph)lOoghave been assigned. Electrophilic attack by
Figure 26 Structure of Ph,SnSnPh,

(Reproduced by permission from 2. anorg. Chem., 1973,396,81)
CX3C02H (X = C1 or F) on hexaphenyldigermane cleaves either 1 or 2
phenyl groups, forming Ph3GeGePh2(02CCX3)and [Ph2(X3CC0,)Ge],,
which are readily converted into the corresponding halides Ph,GeGePh,X
and XPh,GeGePh,X by their reactions with Six, (X = C1 or Br) or strong
mineral acids HX (X = F, C1, Br, or I).loo7The crystal structure of Ph,SnSnPh,
has been determined (Figure 26); r(Sn-Sn) = 2.770A, mean r(Sn-C) =
V. F. Traven and R. West, J. Amer. Chem. SOC.,1973,95,6824.
loo*
H. Sakurai, M. Kira, and T. Uchida, J . Amer. Chem. SOC.,1973,95, 6825.

F. Hofler and E. Hengge, Monafsh., 1972,103, 1506.
loo6F. Hofler and E. Hengge, Monatsh., 1972, 103, 1513.
loo6F. Hofler, Monatsh., 1973, 104,694.
loo7F. Glockling and R. E. Houston, J.C.S. Daltorz, 1973, 1357.
loo3
loo4
386
2.180 A. Ph6Sn2is isomorphous with the corresponding lead compound, but

not with Ph6Ge2.1008
Bonds to Group 111 MetaZs. The reaction of [Ph,SiI4 with lithium in THF
causes ring fission to give (80), which could be isolated as its THF adduct.
Treatment of (80) with CI,BNMe2 resulted in the formation of the heterocycle (81).loo9
PhzSi-SiPh2
Li
PhzSi-SiPh2
THF
PhzSi-SiPh2
Ph,Si
C12BNMez
SiPh2
-2Lic
PhzSi-SiPh2
I I
Ph2Si
SiPhz
\Li
Zi
(80)
NMea
(81)
Boron trichloride reacts smoothly with l-SiH,B,H, to yield l-(CIH,Si)B,H,

in essentially quantitative yield.lO10Chlorovinylsilanes and alkylchlorovinylsilanes silylalkylate 0-,m-,and p-carbaboranes in the presence of AICl,. The
silylalkylation proceeds at a B-H bond of the carbaborane nucleus with the
formation of silicon-containing B-substituted carbaboranes, e.g.:loll
HCBIOHIOCH H2C=CHSiCI3
AlCl3
HCB~OH~O-~(CH~CH~S~CI~)~CH
n = 1,2, or 3.
The reaction of sodium dicarbahexaborane with Me,SnBr or Me,PbC1 in

THF forms the respective p- trimethylmetal-dicarbahexaborane(8). From
spectroscopic data, the structures (82) are proposed. Their reactions with DCI
CH3
generate p-DCzB4H,, with no evidence of terminal B-D bonds. Sodium

hydride treatment of p-Me,Si-C,B,H, involves bridge deprotonation and
bridge-to-terminal silicon migration, giving the 4-Me3SiC2B4H, anion ;
looBH.
Preut, H. J. Haupt, and F. Huber, Z . anorg. Chem., 1973, 396, 81.
E. Hengge and D. Wolfer, Angew. Chem. Internat. Edn., 1973 12, 315.
loon
C. Geisler and A. D. Norman, Inorg. Chern., 1972,11,2549.

F. Mironov, V. 1. Grigos, S. Ya. Pechurina, and A. F. Zhigach, J. Gen. Chem.
(U.S.S.R.), 1972,42,2577.
loloT.
loll V.
Elements o j Group I V
387
O=BH
08 CH
R 8 CH3
Figure 27 Reaction sequencefor the formation of bridge, terminal-disubstituted

derivatives from p-Me3Si-CzB4H7
treatment of this ion with DCl gives ,u-D-4-Me3SiC,B4H6and with Me3SiCl

yields ,u,4[Me3Si]2-C,B4H6 (Figure 27). The reaction of p-Me3Ge-C,B,H7
with NaH followed by Me3SiC1gives a bis(carbaborany1)species of apparent
composition (C,B,H,),GeSi,Me,. In contrast, p-Me3Sn-and p-Me3Pb-C2B4H7
~ with SiHzClz
are nearly inert toward NaH. The reaction of C 2 B 4 H ion
yields ,u,,u-SiH,-(C2B4H7),, which at 100 OC changes to 4,4-SiH2(C2B4H7)2.
Proposed structures for the two isomers of the former are shown in Figure 28.
With MeH2SiCl and cyclotetramethylenedichlorosilane the C,B,H- ion gives
p-(MeH,Si)C2B4H, and p- [(CH,),SiCl]C,B,H,,
respectively; the latter
0 RH
a C H
OH
Figure 28 Proposed structures of the two possible geometric isomers of

p>p-SiH2-(CzB4H7)z
26
388
compound rearranges to the 4-isomer at 220C.10121.r. spectra have been

reported for organosilicon derivatives of m-carbaborane.113IIB and Il9Sn
chemical shifts of some organotin derivatives of o-, rn-, and p-carbaboranes
have been obtained by heteronuclear double resonance.l0l4The vibrational,
l H and llB n.m.r., and Mossbauer spectra of some trimethylstannyl-l,3diaza-2-boracycloalkaneshave been reported.115 The trimethyl derivatives of
the Group III metals, MMe, (M = ByAl, Ga, In, or TI), react with LiSNMe,
in DME forming the species Li [SnMe3MMe,].l0l6Et3Tl and (M%SiCH,),SnH
react at -10 to -20 O C to give [(Me,SiCH,),Sn],Tl, which reacts with
mercury to give thallium metal and [(Me,SiCH,),Sn],Hg. Dibromoethane
and [(Me,SiCH,),Sn],Tl give ethylene and (Me,SiCH,),SnBr, and benzoyl
peroxide affords TlOBz and (M~,S~CH,),S~OBZ.~O~~
Transition-metal Derivatives of Silicon, Germanium, Tin, and Lead.-The
silylation of (C,H,)TiCl, with SiH3K yields the olive-green, benzene-soluble
Figure 29 Structure of [(C,H,) ,T iSiH 2]

(Reproduced by permission from Chem. Ber., 1973,106,1747)
compound [(C,H,),TiSiH,],. The molecule consists of two (C,H,),Ti units
linked by two SiH2 bridges. The TiSiTi bond angle (102.8') is somewhat less
and r(Si-H) = 1.65 A
than the tetrahedral value; r(Si-Ti) = 2.159
(Figure 29).lol8When (C,H&Ti(GePh,), (83) is heated in DME, toluene, or
THF at 100 OC for 40 h, Ph,GeH (0.75 mole) and Ph,Ge (0.12 mole) are
formed, together with the thermally stable paramagnetic (C,H,),TiGePh,
l0l2
A. Tabereaux and R. N. Grimes, Irtorg. Chem., 1973, 12,792.

P. Dorofeenk, N. V. Kozlova, A. L. Klebanskii, and V. F. Gridina, J. Gen. Chem.
lol3 L.
(U.S.S.R.),1973, 43, 297.

P . Tupchauskas, V. I. Stanko, Yu. A. Ustynyuk, and V. V. Khrapov, J. Struct.
Chem., 1972, 13,823.
E. B. Bradley, R. Herber, P. J. Busse, and K. N. Niedenzu, J . Organometallic Chem.,
1973, 52,297.
A. T. Weibel and J. P. Oliver, J . Amer. Chem. Sac., 1972,94, 8590.
G. S. Kalinina, E. A. Shchupak, 0. A. Kruglaya, and N. S. Vyazankin, Izoest.
Akad. Nauk S.S.S.R., Ser. khim., 1973, 1 1 86.
G. Hencken and E. Weiss, Chem. Ber., 1973, 106,1747.
lol4 A.
115
lol'
lol*
389
(84). Treatment of the latter with an equivalent amount of HCl in dioxan
results in the evolution of hydrogen and oxidation of the titanium to give
(C,H,),TiCl(GePh,) (85). Prolonged passage of HCl through the reaction
mixture causes Ti-Ge bond fission, giving (C,M,),TiCl, and Ph,GeH.
Cleavage of the Ti-Ge bonds in (83) and (85) is also accomplished by carbon
tetrachloride in benzene; Ph,GeCl and hexachloroethane are also produced.
Sodium methoxide solution cleaves both the Ti-Ge and Ti-C5H5 bonds of
(83), (84), and (85), giving cyclopentadiene and Ph,GeH.l0lg

The binuclear carbonyls M2(CO)10 (M = Mn or Re), Mn,(CO),(PPh,),,
[Fe(C,H,)(CO),],, and [M1(C,H,)(CO),], (M1 = Mo or W) react with
SiF,H at 165-170 "C to form the trifluorosilyl derivatives F,iM(CO),,
FqSiMn(CO),(PPh,), FqSiFe(C,H,) (CO), , and Fe3SiM1(C,H,) (CO),.1020
Trimethyltin derivatives of manganese, molybdenum, iron, cobalt, and
nickel are also obtained by the reactions of bimolecular metal carbonyls with
(Me,Sn),O or (Me,Sn),N, viz.
+
+
+
+
+ (O,?)
+ (N,?)
+ (O,?)
+ (N,?)
+ (O,?)
+ (N,?)
(Me,Sn),O
[(~-C,H,>MO(CO),]~
3 2Me,SnMo(CO),(r-C5H,)
2(Me,Sn),N
3 [(~-C,H,)MO(CO),~~
3 6Me3SnMo(CO),(r-C51-a,)
(Me,Sn),O
[(T-C,H,)F~(CO),], -+ 2Me,SnFe(CO),(.rr-C5H5)
2(Me,Sn),N
3 [(r-C5H5)Fe(CO),], 4 GMe,SnFe(CO),(?;-C,H,)
(Me,Sn),O
[(rr-C,H,)NiCO], 3 2Me,SnNi(CO)(n-C5H,)
2(Me,Sn),N
3 [(T-C~H~)N~CO],
3 6Me3SnNi(CO)(~-C5H5)
(Me,Sn),
Mn,(CO)lo 3 2Me,SnMn(CO),
(O,?)
2(Me,Sn),N
3Mnz(CO),,, + GMe,SnMn(CO),
(N,?)
(Me,Sn),O
Co,(CO), 3 2Me,SnCo(CO),
(O,?)
2(Me3Sn),N
3Co,(CO), -+ 6Me,SnCo(CO),
(N,?)
+
+
+
+
+
+
+
+
+
Collman has investigated the formation of metal-metal bonded oligomers

using hydrido-germanium- and -tin-metal carbonyl derivatives, which were
first synthesized by the reduction of the corresponding tin and germanium
chlorides with BuiAlH in hexane. The results of coupling reactions are
summarized in Scheme 25.1OZ2
The reaction of H,GeBr with NaRe(CO), affords H,GeRe(CO),, accompanied by a very low yield of a second product, tentatively identified as
GeH2[Re(CO),],.1023 ReSnL,Cl,,H,O (L = thiourea) is prepared by allowing
G. A. Razuvaev, V. N. Latyaeva, G. A. Vasil'eva, L. I. Vyshinskay, and G. Ya.
Mal'kova, Doklady Akad. Nauk. S.S.S.R.,1972,206, 805.
M. E. Redwood, B. E. Reichert, R. R. Schrieke, and B. 0 . West, Austral. J. Chem.,
1973'26,247.
E. W. Abel and M. 0. Dunster, J. Organometallic Chem., 1973, 49, 435.
J. P. Collman, J. Hoyano, and D. W. Murphy, J . Amer. Chem. SOC.,1973,95,3424.
K. M. Mackay and S. R. Stobart, J.C.S. Dalton, 1973,214.
l0ln
loZ2
loZ3
390
H2Sn[Mn(C0)51z -I- COz(c0)e
EtSnPh,
+ HGePhz[Mn(CO),]
25 "C
---+
[(OC)&!o] Sn[Mn(CO)b]2
25 "C
Ph
I
Ph3SnGeMn(CO)s
Ph
HGePh&Mn(CO),]
hv
Phn
/Ge\
(OC)4MnG
'e
'
Mn(C0)4
Ph2
2HGePh2[M(CO)s]
+ Fe2(COh
[( 0C), MI Ph Ge
0
Scheme 25
HReO, in 3N hydrochloric acid to react with thiourea and tin(I1) chloride in

10N-HC1.1024
The crystal structures of two Si-Mn bond compounds have been determined. In tris(trimethylsily1)silylmanganese pentacarbonyl, (Me,Si),SiMn(CO),,the manganeseis octahedrally co-ordinated and the silicon tetrahedrally
(Figure 30). The carbonyl and trimethylsilyl groups appear to be so orientated
as to minimize energy due to non-bonded interactions. The Si-Mn bond
distance is 2.564 A and has no multiple character; the mean Si-Si and Si-C
bond distances are 2.374 and 1.92 A, re~pective1y.l~~~
The structure of di-pdiphenylsilyl-bis(tetracarbony1manganese) may be described as a dioctahedral structure formed by two cis-Mn(CO), groups symmetrically linked by
lo2*
1025
V. G . Kuznetsov, G. N. Novitskay, P. A. Kozmin, and V. V. Borisova, Zhur. neorg.

Khim., 1 9 7 3 , 1 8 , 1135.
B. K. Nicholson, T. Simpson, and W. T. Robinson, J . Organometallic Chem., 1973,
47,403.
391
Elements of Gvoup IV
C(7)
Figure 30 Structure of (Me,Si),SiMn(CO),

(Reproduced by permission from J. Organometallic Chem., 1973,47,403)
two Ph,Si groups (Figure 3 1). The crystallographically imposed site symmetry
of a two-fold axis passing through the two manganese atoms, and a mirror
plane through the two silicon atoms and bisecting the Mn-Mn bond,
requires the Mn2Si2ring to be planar. The formation of a Mn-Mn bond is
strongly suggested by the acute MnSiMn bond angle (73.4') and the Mn-Mn
Figure 31 Structure of [Ph,SiMn(CO),],

(Reproduced by permission from J. Amev. Chem. SOC.,1973,95,783)
392
bond distance r2.871 A; cfi 2.923 8, in Mn,(CO),,]. The Si-Mn and Si-C
bond distances are 2.402 and 1.892 A, respectively.1026
The reaction between Me,SnH and Mn2(CO)1, affords poor yields of
Me,SnMn(CO),. The complex is unaffected by water, methanol, and aqueous
NaOH, but quantitative cleavage of the Sn-Mn bond occurs with 1,2dibromoethane and HgCI,, and with RHgX (R = Me or Ph; X = Cl or Br)
to give products dependent on R and X. Displacement of one methyl group
from Me,SnMn(CO), takes place with CF,COCl and HSiCl,, but SnCl,
cleaves all three tin-carbon b 0 n d s . 1 ~Iodine
~ ~ reacts with Me,SnMn(CO),,
(CH,=CHCH,),SnMn(CO),, Me,SnFe(C,H,)(CO),, and Me,Sn [Fe(C,H,)(GO),], to cleave the metal-metal bonds, although in the case of the trialkyltin derivative,some Sn-C bondcleavageoccurred. Me,SnFe(C,H,)(CO)2
reacted with MeHgCl in [2H6]DMS0to give initially MeHgFe(C,H,)(CO),
and Me,SnCl, which subsequently gave Me,Sn, Me,Hg, Hg[Fe(C,H,)(CO),],,
and ClHgFe(C,H,)(CO),. Me,Sn [Fe(C,H,)(CO),], and Me,SnMn(CO),
react similarly.1028The Sn-Mn1029J030 and Sn-Fe1030 bonds have been
studied by Mossbauer spectroscopy. Manganese-55n.m.r. chemical shiftshave
been reported for several Mn-M (M = Si, Ge, Sn, or Pb) bonded comp o u n d ~ The
. ~ ~vibrational
~~
spectra of triphenyltin-manganese, -iron, and
-rhenium carbonyl complexeshave been examined in detai1.1032-1034The He (I)
photoelectron spectra of silyl and germyl derivatives of manganese, rhenium,
and cobalt carbonyls show bands attributable to transition-metal unshared
&electrons (8-10 eV), the M-H
o-bonding levels from silicon and
germanium np orbitals (1 1-12 eV), and the carbonyl groups (13-19 eV).1035
The photolytic reaction of tin(n) chloride with M(CO), (M = Cr, Mo, or
W) in THF results in the formation of the complexes Cl,Sn[M(CO),],,nTHF,
which are transformed into the dihydrates C1,Sn [M(C0),],,2H20 when
treated with water.1036Tin(n) halides insert into the M-M bond of the
dimers [(C,H,)M(CO),], (M = Cr, Mo, or W). As well as the [(C5H5)M(CO,),],SnX, (X = F, C1, Br, or I) derivatives, the complexes (C,H,)M(CO),X and (C,H,)M(CO),SnX, may be formed, consistent with the
availability of two reaction routes: direct insertion, and an indirect route
proceeding via the (C,H,)M(CO),SnX, compounds as intermediates. The
G. L. Simon and L. F. Dahl, J. Amer. Chem. SOC.,1973, 95,783.
R. A. Burnham, F. Glockling, and S. R. Stobart, J.C.S. Dalton, 1972, 1991.
Io2* R. M. G. Roberts, J . Organometallic Chem., 1973, 47, 359.
l o 2 0 S. R. A. Bird, J. D. Donaldson, A. F. le Holding, B. Ratcliff, and S. Cenini, Inorg.
Chim. Acta, 1972, 6 , 1379.
l o 3 0 G. M. Bancroft, K. D. Butler, A. T. Rake, and B. Dale, J.C.S. Dalton, 1972, 2025.
lo31 G. M. Bancroft, H. C. Clark, R. G. Kidd, A. T. Rake, and H. G. Spinney, Inorg.
Chem., 1973,12,728.
1032 H. Buttery, S. F. A. Kettle, G. Keeling, I. Paul, and P. J. Stamper, J.C.S. Dalton,
1972,2487.
loxi S . F. A. Kettle, I. Paul, and P. J. Stamper, J.C.S. Dalton, 1972, 2413.
1034 R. A. Burnham and S. R. Stobart, J.C.S. Dalton, 1973, 1269.
1036 S. Cradock, E. A. V. Ebsworth, and A. Robinson, J.C.S. Dalton, 1973, 22.
1038 G. K. I. Magrnedov, V. G. Syrkin, and L. V. Morozova, J. Gen. Chem. (U.S.S.R.),
1973, 43,447.
lo2'
393
particular route adopted depends on X, M, the solvent, and the presence,
or not, of light. From the reaction between (C,H,)M(CO),SnX, and
[(C,H,)M(CO),], (X = C1, Br, or I; M, M = Cry Mo, or W), the mixed
complexes [(C,H,)M(CO),] [(C,H,)M(CO),]SnX, may be obtained. The
[(C5H5)Fe(CO),][(C,H,)M(CO),]SnX, complexes are prepared ~ i m i 1 a r l y . l ~ ~ ~
U.V. irradiation of W(CO), and Si21, in pentane leads to the formation of
dimeric [(OC),WSiI,],, for which the structure (86) in which iodine atoms
bridge silicon atoms is proposed.lo3*The hydrido-trimethylstannyl complexes (C,H,)Ta(H),SnM%, (C,H,),Mo(H)SnMe,, and (C,H,),W(H)SnMe,
have been prepared from Me,SnNMe, and the appropriate transition-metal
hydride. The reactions of the molybdenum and tungsten complexes with
dimethyl acetylenedicarboxylate yielded the complexes (C,H,),M(SnMe,)[-C(C0,Me) =CHCO,Me]. With organic halides, the analogous halides
(C,H,)MClSnMe, are formed.1039 The tin-tungsten complexes (C,H,)W(CO),(L)SnMe, (L = phosphine or phosphite) have been obtained by the
usual substitution method from the carbonyl anion and Me,SnC1.1040
The reaction between H,GeCl and Na,Fe(CO), yields (GeH,),Fe(CO),
(87) and (GeH,)HFe(CO), (88) ; NaFe(C,H,)(CO), gives (H,Ge)Fe(C,N,)(CO),. Treatment of (87) with HCl gives (88); with HgCl,, Fe-Ge bond
cleavage occurs and H,GeCl, GeH,, and HCl are formed.lo41The metallic
heterocyclic compounds [R,MFe(CO),], (M = Ge, Sn, or Pb) undergo
facile homolytic cleavage of the M,Fe, ring system with weak bases to
Fe(CO),. The relative cleavage
produce complexes of the type (base)R,M
propensity is Ge > Sn > Pb and pyridine > acetone > THF > diethyl
ether.1042[(C,H,)(CO),Fe]SnCl, reacts with sodium sulphide (Na2S4) or
potassium sulphide (K2S5)to give the complex (89).1043Oxidative-elimination
reactions occur when SnX, (X = C1 or Br) reacts with Fe(CO)&Ph, (E = P,
--+
(89)
Hackett and A. R. Manning, J.C.S. Dalton, 1972,2434.
G . Schmid and R. Boese, Chem. Ber., 1972, 105, 3306.
D. H. Harris, S. A. Keppie, and M. F. Lappert, J.C.S. Dalton, 1973, 1653.
T. A. George and C. D. Turnipseed, Inorg. Chem., 1973, 12,394.
S. R. Stobart, J.C.S. Dalton, 1972, 2442.
T. J. Marks and A. R. Newman, J . Amer. Chem. SOC.,
1973,95,769.
C. Ungurenasu, G. Stiubiano, and E. Streba, Synth. Inorg. Metal-Org. Chem., 1973,
lo3 P.
1038
1038
lo40
lo41
1042
1043
3,211.
394
Inorganic Chernistry of the Main-group Elements
As, or Sb), resulting in the formation of the non-ionic, hexa-co-ordinate

The
derivatives Fe(CO), (X)(EPh,) (SnX,) containing Fe-Sn
trihalogeno-germanium and -tin, -iron derivatives (C,H,)Fe(CO)2MX,
(M = Ge or Sn; X = C1 or Br) react with [(C,H,)Ni(CO)], to form the
57Fe and l19Sn
trinuclear complexes (C,H5)Fe(CO),MX,Ni(CO)(C5H,).1045
Mossbauer data have been reported for the complexes cis-(OC),F(X)SnX,
Figure 32 Structure of Ru2(CO),SiMe,(C,H,SiMe,)

(Reproduced from J.C.S. Chem. Cornrn., 1973, 727)
(X = C1, Br, or I), and cis- and tr~zns-(OC)~Fe(SnX,)~.~~~~
From line asymmetries in the 57Feand l19Sn Mossbauer spectra of (Fe(SnC1,) [P(OMe),],)+
BPhy, Bancroft has deduced that the signs of the quadrupole splitting for
both nuclides are the same and po~itive.l~*~
The crystal structure of (PhCGCPh)(C,H,)(CO)FeSnPh, has been determined (R = 17 %) ; r(Fe-Sn) =
2.56 A, mean r(Sn-C) = 2.2, A.1o4sDipole-moment data are available for
several Sn-Fe-bonded compounds.10*9~1050
1044
1045
T. Takano, Bull. Chem. SOC.

Japan, 1973, 46, 522.
L. K. Thompson, E. Eisner, and M. J. Newlands, J. Organometallic Chem., 1973,56,
327.
1046 N. Dominelli, E. Wood, P. Yasudev, and C. H. W. Jones, Inorg. Nuclear Chem.
Letters, 1972, 8, 1077.
1047 E. T. Libbey and G. M. Bancroft, J.C.S. Chem. Comm., 1973, 503.
1048 V. E. Shklobed, V. V. Skripkin, A. I. Gusev, and Yu. T. Struchkov, J. Struct. Chem.,
1972, 13,744.
1049 S . Sorriso, G . Distefano, and A. Foffani, J. Organometallic Chem., 1973, 47, 139.
1050 Yu. V. Kolodyazhnyi, V. V. Skripkin, N. E. Kolobova, A. D. Garnovskii, B. V.
Lokshin, 0. A. Osipov, K. N. Anisimov, and M. G. Gruntfest, J. Struct. Chem., 1972,
13, 148.
395
Substituted cycloheptatrienes, 7-RC7H,, react with [Ru(CO),(SiMe,)], to

afford fluxional complexes [Ru,(CO),(SiMe,)(C,H,R)] (R = H, Me, Ph, or
C,H,) (90), in which the C, ring bridges both ruthenium atoms. The crystal
structure of a minor reaction product (R = SiMe,) is shown in Figure 32;
r(Ru-Si) = 2.456
The structure of [(Me$i)(CO),RuSiMe,], is shown
in Figure 33. The two Me,Si groups bridge the (Me,Si)(C0)2Ru residues
Figure 33 Structure of [(Me,Si)(CO),RuSiMe,],

(Reproduced from J.C.S. Dalton, 1972,2512)
[v(Ru-Si),i,,
= 2.391, 2.491 A]. The distortions of the Ru2Si, ring and the
Ru-Ru bond distance (2.96 A) argue for the presence of a Ru-Ru bonding
i n t e r a ~ t i 0 n . lReduction
~~~
of Os,(CO),, with sodium in liquid ammonia
affords a cream solid which reacts with metal halides to afford the complexes
Os(CO),X2 (X = H,Ge, Ph,Sn, or Me,Pb). Low yields of the hydridospecies Os(CO),(X)(H) (X = H,Ge or SnMe,) were also formed. With
Me,SnCl,, the Sn-0s heterocycle [Os(CO),SnMe2], is formed.1053
When Me,SiCo(CO), is heated to 105 "Cfor 50 h, migration of the Me3Si
group from cobalt to oxygen takes place to give M~,S~OCCO,(CO)~
and
(Me,SiOC),Co,(CO),. The former compound is also formed in high yields in
1 h at room temperature together with cis- and trans-Me,SiOCH=CHEt
by the reaction of
and cis- and trans-Mq,SiOCH=CH(CH,),OSiMe,
Me,SiCo(CO), with THF. (Me,SiOC),Co,(CO), may be considered as being
with the structure (9 1).1054
derived from (M~,S~OC=COS~M~,),CO~(CO)~,
A. Brookes, J. Howard, S. A. R. Knox, V. Riera, F. G. A. Stone, and P. Woodward,
J.C.S. Chem. Comm., 1973, 727.
los2 M. M. Crozat and S. F. Watkins, J.C.S. Dalton, 1972,2512.
1053 R. D. George, S. A. R. Knox, and F. G. A. Stone, J.C.S. Dalton, 1973, 972.
lob4 W. M. Ingle, G. Preti, and A. G. MacDiarmid, J.C.S. Chem. Comm., 1973, 497.
lo51
396
Pico
Me3Si-Ru
? \c
(90)
0
(91)
= OSiMeo
The tin atom in BrSn[Co(CO),], is surrounded tetrahedrally by the bromine

atom and three Co(CO), groups (Figure 34); r(Sn-Br) = 2.52A and
Figure 34 Structure of BrSn[Co(CO),],

(Reproduced by permission from J. OrganometalZic Chem., 1973, 52,293)
r(Sn-Co) = 2.60 A.1055The structure of bis(pentane-2,4-dionato)(heptacarbonyldicobalt)tin(rv), (C,H70,)2SnCo,(CO)7, is shown in Figure 35. The
tin atom is six-co-ordinated by the two acetylacetonate residues and the
dicobalt-heptacarbonyl residue, forming a three-membered SnCo2. The
Sn-0 bond distances are in the range 2.09-2.15 A, and the mean Sn-Co
1055
R.D. Ball and D. Hall, J . Organometallic Chem., 1973, 52, 293.
397
Figure 35 Structure of (C,H,O,),SnCO,(CO),

(Reproduced by permission from J. OrganometaZZic Chem., 1973, 56,209)
distance is 2.577 A.1o5G
[Me,SnCo(CO)(C,H,)], contains a four-membered
Sn,Co, ring (Figure 36) with tetrahedrally co-ordinated tin and octahedrally
co-ordinated cobalt atoms; r(Co-Sn) = 2.542A and mean r(Sn-C) =
2.20
The Mossbauer spectra of four-co-ordinate Sn-Co bonded
compounds have been r e ~ 0 r t e d . lIn
~ ~THF-ether,
~
Ph,SnLi phenylates
(R,PPh),NiCl, (R = Et or Bu) to afford (R,PPh),NiClPh, but with (Ph3P),CoCl, in TWF at - 1 O O C reduction takes place and (Ph,P),CoCl and
Ph,SnSnPh, are formed. NaSnPh, reacts with (Ph,P),NiCI2 to give mixtures of
Figure 36 Structure of [Me,SnCo(CO)(C,H,)],

1056
lo5'
1068
R. D. Ball and D. Hall, J . Organometallic Chem., 1973, 56, 209.

J. Weaver and P. Woodward, J.C.S. Dalton, 1973, 1060.
G. M. Bancroft and K. D. Butler, J.C.S. Dalfon, 1973, 1694.
398
Inorganic Chainistry of the Main-group Elements
compounds of the types Na,[(Ph,P),,Ni(SnPh,),],yTHF

( x = 1,2, 3, or 4),
and with Ni(cyclo-octa-l,5-diene), to displace cyclo-octadiene. Ethene is
similarly displaced from (Ph,P),Ni(C,H,) by LiSnPh,, affording the complex
Li2[(Ph3P)2Ni(SnPh3),],5THF.1059
Glockling has synthesized a wide range of
silicon-, germanium-, and tin-nickel complexes of the type (C,H5)R3MNi(L)
(R = halide, alkyl, or aryl; M = Si, Ge, or Sn; L = R3P, R,As, or
C6H1,NC). Mono-alkyl- or -aryl-ation of Ni-MCl, (M = Ge or Sn) may be
achieved by using EtpPb or Ph,Hg. With excess phosphine, the neutral complexes are converted into salts of the type [(C,H,)(L),Ni]MX, (M = Ge or
Sn; X = halide).lo60Aqueous CoC1,,6H20 treated with HCl, tin(I1) chloride,
and ethylenediamine (en) affords pink octahedral [Co(SnCl,),(enH),], which
when heated to 105 "C gives blue tetrahedral (enH),[Co(SnCl,),], which on
further heating to 225 "C is transformed into a green isomer. Mixed halogenotrihalogenotin complexes which behave similarly may be obtained by
analogous methods.10G1-1063
Silylacetylene and silyl perfluoromethylacetylene react with transHPt(PEt,),Cl to give complexes of the form trans-YC=CSiH,Pt(PEt3),Cl
(Y = H or CF,). The same acetylenes react with trans-I,Pt(PEt,), at low
temperatures, to give initially complexes of six-co-ordinate platinum,
HPt(SiH,C=CY)(PEt,),I,, which decompose to give YC=CSiHIPt(PEt,),I
(ref. 1064). Hexachlorodisilane adds oxidatively to Pt(PPh,), to give
Pt(PPh,),(SiCI,),,but is not , as previously reported, dechlorinated by PPh,
under completely anhydrous conditions. However, if a trace of water is added
to the reaction mixture of Pt(PPh,),(SiCI,), and PPh,, the yellow 'dechlorination' product is formed, which is most probably an impure hydrolysis
product. Si2C16also reacts in the same fashion with [(C,H,)(CO),Mo], to give
Mo(CO),(C,H,)SiCl, and with Ir (Cl)(CO)(PPh,) to give Ir (Cl)(CO)(PPh,),The monomeric,
(SiCI,),. Reaction with Fe(CO), affords [(CO),FeSiC12]2.1065
non-ionic complex (PPh,),(CO)(CI)Ir(SnCl,) forms rapidly when transIr(Cl)(CO)(PPh,), and SnCl, are mixed in an organic solvent. MeSnCI,
reacts similarly to form (PPh,),(CO)(Cl)Ir(SnMeCl,). The presence of two
carbonyl stretching frequencies in the i.r. spectrum indicates the presence of
isomers. The available data suggest the occurrence of an isomerism arising
from the rapidly equilibrating oxidative-addition (92) and donor-adduct
(93) isomers.loB6
loSQ
lo60
loB1
lo6'
1063
loB4
1065
1066
P. Muller, E. Uhlig, and D. Walther, Z. Chem., 1973, 13, 141.

F. Glockling and A. McGregor, J. Inorg. Nuclear Chem., 1973, 35, 1481.
M. Rrezeanu and L. Patron, An. Univ. Bucuresti, Chim., 1972, 21, 71 (Chem. Abs.,
1973, 79, 38 086b).
M. Brezeanu and L. Patron, An. Univ. Bucuresti, CJzim., 1972,21, 121 (Chem. Abs.,
1973, 79, 38 087c).
M. Brezeanu and L. Patron, Rev. Roumaine Chim., 1972, 17, 1857.
D. W. W. Anderson, E. A. V. Ebsworth, J. K. MacDougall, and D. W. H. Rankin,
J . Znorg. Nuclear Chem., 1973, 35,2259.
F. Glockling and R. E. Houston, J . Organometallic Chem., 1973, 50, C31.
C. B. Dammann, J. L. Hughey, D. C. Jicha, T. J. Meyer, P. E. Rakita, and T. R.
Weaver, Inorg. Chem., 1973, 12,2206.
' L
399
P1
(92)
'co
L
'
'
co
(93)
Palladium and platinum tetrakis(tripheny1phosphine) undergo oxidative

addition with hexaphenyldilead to give the complexes M(PPh,),(PbPh3),
(M = Pd or Pt). The lead derivative slowly decomposes in CH,Cl, to give
cis-Pt(PPh,),(PbPh,)Ph, which is also obtained by treatment of PhLi. The
reaction of Pt(PPh,), with Me,PbPbMe, gives the complex Pt(PPh,),(PbMe,)Me directly. The structure of cis-Pt(PPh,),(PbPh,)Ph is shown in Figure 37.
The co-ordination at platinum is square-planar; the Pb-Pt and Pb-C bond
The l19Sn Mossbauer
distances are 2.698 and 1.844 A, respe~tive1y.l~~~
spectra for trichlorostannyl derivatives of iron(@, ruthenium(rr), rhodium@,
iridium(m), platinum(rr), copper(r), silver(r), and gold(1) have been reported.1068
The reaction of organotin halides with zinc in various solvents has been
studied. Reactive organotin-zinc compounds are initially formed, but the
final products depend on the solvent employed. In aprotic solvents in the
absence of strongly co-ordinating ligands, tetraorganotin compounds are
formed via alkylation or arylation by intermediate organozinc compounds,
produced by 1,Zintermetallic shifts of organic groups in the initial organotinzinc reaction product, and from redistribution and transmetallation reactions,
In the presence of proton donors, the intermediate organozinc compounds
are protolysed to afford hydrocarbons. Strongly co-ordinating ligands
prevent 1,2-migrations, and hexaorganoditin compounds are formed.1069
Triphenylgermanecleaves the Zn-C bonds of Et,Zn in diglyme; EtZnGePh,
is formed at room temperature, whereas at 150 "C, both Zn-C bonds react,
to give Zn[GePh,],. When they took place in (Me,N),PO or DMF, the
reactions afforded the same products but solvated by two molecules of solvent.
EtZnGePh, and acetic acid give Ph,GeH and EtZnOAc, but excess acid
produces Zn(OAc),. EtZnGePh, and ethyl bromide at 100 "C give Et,Zn and
Ph,GeBr, which react further to form Ph,GeEt, ZnBr,, and Et,Zn. The
reaction with dibromoethane was complex, resulting in the formation of
EtBr, Ph,GeBr, C,H,, and ZnBr,. Both Zn-C and Zn-Ge bonds are
cleaved by iodine, giving EtI, ZnI,, and Ph,GeI. One mole of acetic acid
cleaves one Zn-Ge bond of Zn[GePh,], giving Ph,GeH and Ph,GeZnOAc,
but an excess results in the fission of both bonds.1070[(C,F,),Ge],Cd forms
lo6' B.
Crociani, M. Nicolini, D. A. Clemente, and G. Bandoli, J. Organometallic Chem.,

1973,49,249.
1068 R. V. Parish and P. J. Rowbotham, J.C.S. Dalton, 1973, 37.
l o 6F.
~ J. A. des Tombe, G. J. M. van der Kerk, and J. G. A. Noltes, J. Organometallic
Chem., 1973, 51, 173.
V. T. Bychkov, N. S. Vyazankin, and G. A. Vyazankin, Zhur. obshchei Khim.,
1973,43, 793.
Figure 37 Structure of Pt(PPh3),(PbPh3)Ph

(Reproduced by permission from J . Organometallic Chem., 1973,49,249)
P
0
401
1 :1 adducts with Ph,P, (Et,Si),S, (Et,Sn),S, THF, (Et,Si),Se, (Et,Si),Te,
pyridine, (Et,Ge),Sb, 2,2-bipyridyl, Et,Sb, and (CH,NMe2)2, and 1:2
adducts with Et,S and Et2S2.1071
[Et,Ge12Cd reacts with benzaldehyde at 20 C
to deposit metallic cadmium, and form Et,GeOCHPh. With pyridine, cadmium is also deposited and the 4,4-coupled product (94) is formed. Di-
,CH=CH
,CH=CH
>CH-CH
EtlGeN
CH=CH
phenylacetyl is converted into a,cc-bis (trieth yl germy1)st ilbene, Et,GeCPh=CPhGeEt,. Phenylacetylene causes decomposition to Et,GeH, Et,GeC=CPh,
and Cd. The reaction with 1 ,l-diphenylethyleneis complex;cadmium, Et,Cd,,
(2,2-diphenylethyl)diethylgermane, and a difficultly separable mixture of
organogermanes are formed.1072
The thermal decomposition of bis(trimethylsily1)mercury in benzene or
cyclohexane shows second-order kinetics, hexamethyldisilane being the only
major organic product. In toluene, mixed second-order and (pseudo)-firstorder kinetics are observed, giving rise to Me$iH, Me,SiSiMe,, and
Me,SiCH,Ph in approximately equal proportions. Only (pseudo)-first-order
kinetics are observed in anisole, giving 70-88% yields of Me,SiOPh. The
(pseudo)-first-order kinetics appear to arise from bimolecular reaction of the
solvent with (Me3Si),Hg.1073Sulphur and selenium insert into the Hg-Si
and Hg-Ge bonds of [R3MI2Hgand [R,M]HgR to give [R,MX]HgMR,
and R,MXHgR (M = Si or Ge; X = S or Se; R = Et or Pri). Diethyl
disulphide also cleaves the Si-Hg bond of [Et,Si],Hg, forming Et,SiSEt
and mercury. Irradiation of [R,MX]HgMR, causes the elimination of
mercury and the formation of (R3M),E. Metallic lithium cleaves all mercuryligand bonds in [R,MX]HgMR3 and R,MXHgR, giving besides mercury the
lithio-derivative of the ligand.1074Ligand redistribution between (CF,),Hg or
(C,F,),Hg and (Et,Si) H occurs in toluene at room temperature to afford the
2 g
mixed mercurials RHgSiEt, (R = CF3 or C,F,). Reaction with HgF, in
THF results in the formation of mercury and Me,SiF. The same products are
M. N. Bochkarev, V. S. Andreevichev, and N. S. Vyazankin, Izvest. Akad. Nauk
S.S.S.R., Ser. khim., 1973, 702.
1073 V. T. Bychkov, N. S. Vyazankin, N. F. Cherepennikova, and G. A. Razuvaev,
J . Gen. Chem. (U.S.S.R.), 1973,43,626.
1073 C. Eaborn, R. A. Jackson, and R. W. Walsingham, J.C.S. Perkin II, 1973, 366.
1074 E. N. Gladyshev, V. S. Andreevichev, A. A. Klimov, N. S . Vyazankin, and G. A.
Razuvaev, J. Gen. Chem. (U.S.S.R.), 1972,42, 1067.
lo71
402
formed from t he CsF-catalysed decompositionof Et,SiCF,. With Et,SiHgC,F,,

the decomposition yields mercury, Et,SiF, and C2F4. The stannyl-mercurial
[(Me,SiCH,),Sn],Hg reacts with [(CF,),CF],Hg and [(CF,),C],Hg to give,
besides mercury and (Me,SiCH,),SnF, CF3CF=CF2 and (CF,),C=CF,,
respe~tive1y.l~~~
The reaction of (C,F,),GeH with HgR, [R = Et, GeEt,, or
N(SiMeJ,] or Et,Cd gives [(C6F,),Ge],M (M = Cd or Ag). The mercurial
may also be obtained by the displacement of cadmium by metallic mercury
from the cadmium compound, and also by ligand exchange betweenlEt,Ge],Hg and (C,F,)3GeBr.1076 Similar exchange using (C,F,),SnBr yields the mixedmetal mercurial (C,F,),GeHgSn(C,F,),.
Reaction in a 2: 1 ratio leads to the
formation of [(C6F5)3Sn],Hg.1077
The mean dissociation energiesD(Si-Hg) =
20 f.3kcalmol-l [(Et,Si),Hg], D(Ge-Hg) = 8 f 3 kcal mol [(Et,Ge),Hg]
or 17 f 3 kcal mol-l [(Pr:Ge),Hg], have been determined c a l ~ r i m e t r i c a l l y . ~ ~ ~ ~
Bivalent Derivatives of Silicon, Germanium, Tin, and Lead.--SilyZenes. The
formation of high-energy silicon atoms by the nuclear recoil technique in the
presence of buta-l,3-diene gives rise to silylene consisting of 80 % triplet and
20 % singlet. Both configurations add to buta-l,3-diene to give silacyclopent3-ene, as shown in Scheme 26.1079The relative rates of silylene insertion into
methyl-silanesand -germanes in competition with disilane have been measured

in a recirculating flow system. The rates, expressed in terms of relative rate
per M-H (M = Si or Ge) bond available for insertion, found were Me,SiH >
Si,H6 > Me,SiH, > MeSiH, > SiH, > MeGeH,, whilst no insertion products were found with MePH, or CISiH, in competition with Si,H,. Pyrolysis
of trisilane at 330 "C yielded SiH,, SiH,, Si,H,, and Si,H, as primary products. The biradicals :SiH, and :Si,H, have been trapped by Me,SiD and
Si3H,. The relative ratios of normal- to iso-tetrasilane produced from the neat
pyrolysis of Si,H, provide evidence for :SiH, and :Si,H, insertions into both
1075
1076
B. I. Petrov, 0. A. Kruglaya, G . S. Kalinina, N. S. Vyazankin, B. I. Martynov, S. R.

Sterlin, and B. L. Dyatkin, Izuest. Akad. Nauk S.S.S.R., Ser. khim., 1973, 189.
M. N. Bochkarev, L. P. Maiorova, and N. S. Vyazankin, J. Orgartometallic Chem.,
1973,55, 89.
1077
M. N. Bochkarev, L. P. Maiorova, and N. S. Vyazankin, J. Gen. Chem. U.S.S.R.,
1078
G . M. Kol'yakova, I. B. Rabinovich, N. S. Vyazankin, and E. N. Gladyshev, Doklady

Akad. Nauk S.S.S.R.,1972,204,419.
G. P. Gennaro, Y. Y. Su, 0. F. Zeck, S. H. Daniel, and Y. N. Tang, J.C.S. Chem.
Comm., 1973, 637.
1972,42,2344.
1070
403
Si-H and Si-Si bonds.loaOArrhenius parameters for the silylene-insertion

reactions (1 02)-(104) have been calculated.lml The gas-phase reaction of
SiH2
SiH4
Si2H6
(102)
SiH2
H2
SiHa
(1041
OF,COF with difluorosilylene yields (F3SiOSiF,),0.1082 The reaction of

:SiF, with CF3COCl at low temperature yields (95).1083Pyrolysis of hexa-
(95)
chlorodisilane in the presence of 1,3-dienes in a flow system at 500 O C yields

the expected 1,l-dichloro-l-silacyclopent-3-enes.Reaction with cyclopentadiene yields the silahexadiene (96). The reaction with furan is more
(96)
complex,1o84giving (97) and then (98), and eventually (99).

Photolysis of Me,Si(MePhSi),SiMe3 generates methylphenylsilylene
:sic12 -+-
7
- c0 [ -,
>]
/
Cls
(97)
C12Si,
<o
SiC12
:sic*2,
c12
C12Si, ,Sic&.
(98)
(93)
MePhSi: , which can react with cyclohexene to give

The conservation of orbital symmetry in the cycloadditionreactions of tetrafluorodisilylene
lo8O M. D. Sefcik and M. A. Ring, J . Amer. Chem. SOC.,1973,
loa1P. John and J. H. Purnell, J.C.S. Faraduy I , 1973, 1455.
95, 5168.
D. Catrett and J. L. Margrave, Synth. Inorg. Metal-Org. Chem., 1972, 2, 329.

F. D. Catrett and J. L. Margrave, J . Znorg. Nuclear Chem., 1973, 35, 1087.
E. A. Chernyshev, N. G. Komalenkova, and S. A. Bashkirov, Doklady Akad. Nauk
loBa
F.
183
1034
S.S.S.R.,
1972,205, 642.
loS5
27
M. Ishikawa, M. Ishiguro, and M. Kumada, J. Organometallic Chem., 1973,49, C71.
404
PhhiMe
H
(100)
has been discussed.los6Dihalogenosilylenes :Six, (X = Cl, Br, or I) may be

stabilized in the platinum or tungsten complexes (Ph3P)2Pt(SiX2), and
[(CO)5WSi12]2.1087
The latter compound has already been discussed (see
p. 393).lW8The :SiCl, and :SiBr2have been produced by the reaction of the
corresponding silicon tetrahalides and elemental silicon at 900-1 150 'C.
Figure 38 Crystal structure of SnCI2,2H,O viewed along the a-axis. Hydrogen

bonds are indicated by broken lines
(Reproduced by permission from Bull. Chem. SOC.
Japan, 1973,46,1389)
1086
lo87
C . S.Liu and J. C . Thompson, Tetrahedron Letters, 1973, 1581.

G. Schmid, Angew. Chem. Internat. Edn., 1972, 11, 1034.
405
The assignment of the fundamental vibrations in is-. spectra of these species

trapped in Ne, Ar, and N, matrices allowed the calculation of valence force
constants and bond angles (LClSiCl = 105 f 3', LBrSiBr = 109 f 3).10ss
Germnium(u), Tin(Ir), and Lead(1r) Halides and Halide Complexes. The
crystal structures of hydrated tin(@ chloride and bromide, and of anhydrous
tin(@ iodide, have been determined. That of SnC1,,2H20 is a more accurate
redetermination and is shown in Figure 38. The tin atom is pyramidally
(4
(6)
Figure 39 The co-ordination of Sn(2) in SnI, (trkonal-prismatic sites)

co-ordinated by two chlorine atoms and one oxygen atom, r(Sn-0) =
2.33 A, u(Sn-Cl) = 2.50,2.56 A, the bond angles being slightly less than 90'
(86.9,85.0, and 87.9'). The crystal consists of double layers of the monoaquocomplex, with intervening layers of the second water molecules. Both types
of water molecules are linked together by hydrogen bonds of 2.74, 2.79, and
2.80 8, into two-dimensional networks.loaSIn 3SnBr,,H,O, the tin atom is
surrounded by a trigonal prism of bromine atoms, with bromine atoms and
water molecules capping the prism faces. The Sn-Br distances range from
2.77 to 3.68 A, and the Sn-0 distance is 2.35 A.losoSnI, possesses a unique
AX2 layer structure in which the metal atoms occur in two different sites.
Two-thirds of the tin atoms occupy sites similar to those in SnC1, (PbC1,-type)
(Figure 39), whilst the remainder are in PdC1,-type chains which interlock
with the PbC1,-type part of the structure to give almost perfect octahedral
co-ordination at tin (Figure 40). Significant Sn-I distances are all in the
range 3.00-3.25
Enthalpy changes for the vaporization of tin@)
mBG. Maass, R. H. Hauge, and J. L. Margrave, Z . anorg. Chem., 1972,392,295.
loB9
H. Kiriyama, K. Kitaham, 0. Nakamura, and R. Kiriyama, Bull. Chem. SOC.Japan,
1973,46,1389.
10gO
loS1
J. Anderson, Acta Chem. Scand., 1972,26, 3813.

R. A. Howie, W. Moser, and I. C. Travena, Acta Cryst., 1972,3328,2965.
406
chloride and bromide have been measured.1092The far4.r. spectrum of matrixisolated GeBr, has been reported.log3
The structure of NH,SnF, consists of SnF, and NH, groups combined in a
three-dimensionalnetwork by one quadrifurcated and three normal hydrogen
bonds; r(Sn-F) = 2.05-2.21 .$, LFSnF = 83.1-85.9.1094B~ththeredand
the green isomers of [Co(Ph2PCH2CH2PPh2)C1]SnCl,
contain isolated pyramidal SnCl; anions. Some irregularity is found for the bond parameters for
Figure 40 Co-ordination of Sn(1) in SnI, (octahedral sites)

(Reproduced by permission from Acta Cryst., 1972, B28,2965)
the green isomer, probably owing to some disorder. Mean values for the red
isomer are r(Sn-C1) = 2.444 A and L ClSnCl = 94.460.1g5The structure of
the mixed valence germanium fluoride Ge5FI2[(Ge11F2),-Ge1VF,] is shown in
Figure 41. The GeTVatoms [labelled Ge(2) in Figure 411 are surrounded by a
slightly distorted octahedron of fluorine atoms; r(GeIV-F) = 1.71-1.80 A
and LFGeIVF = 8'7.5-92.5". The octahedra are linked, by fluorine-bridging
[F(3) and F(4)], to the two crystallographically distinct Ge'' atoms [Ge(l)
and Ge(3)], which have very similar fluorine co-ordination. The Ge" atoms
are situated at the apices of a distorted square pyramid with fluorine atoms at
the base; r(Ge1I-F) = 1.80-2.45A. The overall structure is built up by
means of fluorine bridging.log6 Tin-119 Mossbauer and X-ray powder
diffractiondata have been reported for a large number of halogenostannates of
the types MSnX,, MX,MSnX3, and MSnX, (M = Na, K, Rb, Cs, or NH,;
S . Ciach, D. J. Knowles, A. J. C. Nicholson, and D. L. Swingler, Inorg. Chem., 1973,
12, 1443.
l o S 3R. J. Isabel, G. R. Smith, R. K. McGraw, and W. A. Guillory, J. Chem. Phys., 1973,
58, 818.
loS4 G . Bergerhoff and L. Goost, Actn Cryst., 1973, B29, 632.
loQ5 J. K. Stalick, P. W. R. Corfield, and D. W. Meek, Inorg. Chem., 1973, 12, 1668.
IoD6 J. C. Taylor and P. W. Wilson, J . Amer. Chem. SOC.,1973,95, 1834.
loB2
407
Figure 41 Crystal structure of Ge,F,, as viewed down the b-axis. The GeIVF,
octahedron is in the centre of the diagram. Atoms Ge(1) and Ge(3)
are Ge'' atoms. The dotted line is the weaker Ge(3)-F(4) interaction of 2.67 A
(Reproduced by permission from J . Amer. Chem. SOC.,1973,95, 1834)
X = C1 or Br) obtained from aqueous and molten MX-SnX, systems.10g7

Two types of product are obtained from cooled CsSnX,-CsSnXi (X,X' =
F, C1, Br, or I) melts: (i) complexes containing tris(ligand)stannate(rI)
species, and (ii) compositions which have cubic or near cubic unit cells
based on the perovskite structure. Mossbauer data for the latter materials
suggest that the tin is in a regular octahedral environment.log8Phases and
compositions obtained from the analogous molten systems CsPbCI,CsPbBr,
and C S P ~ C ~ , B ~ , , - C S S ~ C ~ , are
B ~ ~all
- ~single-phase solid solutions based
on the perovskite lattice with random distribution of tin and lead, and halide
ions.loS9Vapour pressures of molten PbCI, NaCl mixtures have been
measures at 1071 K. Mass spectrometry shows that the complex NaPbC1, is
formed in the vapour. The enthalpy of formation of this compound from
NaCl(g) and PbCl,(g) and the equilibrium constant have been deduced.lloO
S. R. A. Bird, J. D. Donaldson, and J. Silver, J.C.S. Dalton, 1972, 1950.

J. D. Donaldson and J. Silver, J.C.S. Dalton, 1973, 666.
loge J. D. Donaldson, D. Laughlin, S. D. ROSS,
and J. Silver, J.C.S. Dalton, 1973, 1985.
l1O0 H. Bloom, S. R. Richards, and D. J. Williams, Austral. J . Chem., 1972, 25, 2077.
log'
logs
408

The conductivities of fused PbBr,
KBr mixtures, containing up to ca.
90 mole % KBr, have been determined as a function of teanperature.llo1The
electrochemical adsorption of chlorine in the molten PbCI,-KCI salt system
on an active carbon electrode has been studied.llo2 The PbC1,-UCI, and
NaCl-PbC1,-UCl, fusion diagrams have been studied. The former system
forms one eutectic and one chemical compound 4PbC12,UCI,. The primary
crystallization surface of the NaCl-PbC1,-UCl, system consists of five fields,
which form one eutectic and two peritectic points.llo3The KI-SnI, system is a
simple eutectic. In that with RbI instead of KI, there is a 3:2 compound,
and in that with CsI, a 1 :1 compound. In the MI-Pb12 systems, the equilibria
are complicated by the formation of 2: 1 (M = K), 9: 1 and 1 :1 (M = Rb),
and 4: 1 and 1 :1 (M = Cs) compounds.llo4The electronic spectra of some
halogen-lead(@ complexes have been investigated.llo5 A large number of
complexes of the types 2SnCl,,L (L = organic amine), SnCI,,L (L = amine,
amino-acid, urea, or thiourea), and SnC12,2L (L = amine or amino-acid)
have been prepared. The thermal stability decreases in the order 2SnCI,,L >
SnC12,L > SnC1,,2L. Thiourea co-ordinates through the sulphur atom,
whilst urea and the amino-acids co-ordinate via oxygen. The SnCI,,L,HOAc
complexes are formulated as [S~CI,(OAC)]H~N(CH~)~CO,H.~~~~
Tin@) chloride reacts with bis(ferroceny1- and cymantrenyl-)mercury in
co-ordinating solvents such as THF to form bis-(ferroceny1)- and -(cymantreny1)- tin dichloride, respectively.110712-Molybdophosphoricacid is reduced
by tin(1r) chloride in four steps, in each of which one equivalent of SnCI,
is consumed, and the heteropoly anion accepts two electrons.llo8
Oxygen Derivatives of Germunizim(rr),Tin(11),and Lead(@. Germanium(I1)

oxide disproportionates at 415470 "C to germanium metal and germanium(1v) oxide. At 805-835 "C, Ge metal reduces the Ge02 to GeO, which
then sublimes.110gThe reduction of GeO by hydrogen begins at 380 "C. At
380-460 "C the reduction is simple, but above 460 "C the disproportionation
reaction begins, and the reduction becomes reversible.ll10 Tin(@ oxide
disproportionates at 300 "C, and, together with SnO,, unstable Sn,O, is
1101
1102
I1O3
A. J. Easteal and P. H. Khoo, Austral. J. Chem., 1973,26,733.

S . Sterberg, V. Petrescu, and I. Galasiu, Rev. Roumaine Chim., 1972, 17, 1689.
V. N. Decyatnik, Yu. T. Mel'nikov, I. F. Nichkov, and S. P. Raspopin, Russ. J.
Inorg. Chem., 1972, 17, 1461.

I. N. Belyaev, E. A. Shurginov, and N. S. Kudryashov, Rum. J. Inorg. Chern., 1972,
17, 1473.
1105 L. Kolditz, W.Schiller, and J. Kunze, 2. anorg. Chem., 1973, 385, 207.
llo6 T. N. Sumarokova and D. E. Surpina, Teor. Pastuorou, 1971, 323 (Chern. A h . ,
1973, 78, 51 890h).
A. N. Nesmeyanov, T. I?. Tolstaya, and V. V. Korol'kov, Doklady Akad. Nauk
S.S.S.R., 1973,209, 1113.
H. K. El-Shamy and M. F. Iskander, J. Inorg. Nuclear Chem., 1973, 35, 1227.
llo9 A. V. Zagorodnyuk, R. L. Magunov, and I. P. Kovalevskaya, Izuest. Akad. Nauk
l1l0 G . A. Agarkov, L. P. Konysheva, V. A. Ponomarenko, and R. H. Sadykov, Zzuest.
Akad. Nauk S.S.S.R., Metal., 1973, 30.
1104
409
formed, which further decomposes under the same conditions.llll The
Mossbauer spectrum of Sn,O, shows that both SnII and SnIV are present.1112
The transition of tetragonal PbO to the orthorhombic modification starts
after 5 h at 470480 OC, but is still incomplete after 70 h.1113 Both oxygen
and nitric oxide oxidize lead to a-PbO, the reaction with oxygen being the
faster.1114The rate at which a highly supersaturated lead vapour condenses
and oxidizes to yield smokes of lead and PbO has been investigated in a
shock-tube study of the decomposition of tetramethyl-lead in argon and in
air.1115 The photoproperties of anodized lead monoxide have been studied.1116
Several tin and lead ternary oxides have been studied. Diamagnetic and
semiconducting P-SnWO, has been obtained from SnO and WO, in evacuated
silica capsules at 600-900 'C. In the crystal, the tungsten atom is located in
a fairly regular oxygen tetrahedron. The tin atom is co-ordinated by six
oxygen atoms, forming three short (2.21 A) and three long (2.81 A) bonds.1117
Partially oxidized tin(r1) niobate and tantalate pyrochlores are homogeneous
cubic phases. Mossbauer spectroscopy shows the presence of both Sn" and
SnIV oxidation states. Each valence state is segregated on its own crystallographically distinct sublattice as a consequence of the different ionic radii.
The formulae of the two non-stoicheiometric pyrochlores based on Mossbauer-evaluated population ratios are Sn,2,(Sn4,+B~+,)0,-(5i2)n (B = Nb or
Ta; n = 0.18--0.20).111s Na2PbOz shows a layer lattice; perpendicular to
(100) there follow layers with the sequence (Nal/2Pb,/2)ONaO(Nal/2Pbl/2)
*
- - (Na,~,Pbl~,)ONaO(Nal~,Pbl~2).1119
At 50 O C in the B,O,-PbO-H,O
system, only lead tetraborate Pb0,2B20,,3H,O is present, whereas at 100 OC
the borates 4Pb0,5B20,,2.5H20, Pb0,2.5B,0,,2H20, and 3Pb0,10B,O3,9H20 occur.1120 The initial stages of the formation of thin films of Pb2Si0,
from PbO and SiO, have been studied.1121Perovskite lead@)titanate, PbTiO,,
may be obtained by the careful decomposition of the complex Pb(H,O),TiF,
(from PbCO, and H2TiF,).1122 Direct fusion of PbO and PbCrO, yields
Pb2Cr0,, which is isomorphous with lead penta-oxosulphate and -selenate.l12,
The synthetic chervetite has a dichromate-type structure, with the V204G. Murken and M. Tromel, 2. anorg. Chem., 1973,397, 117.
K. Hasselbach, G. Murken, and M. Tromel, 2. anorg. Chem., 1973, 397,127.
llls E. M. Dragulin, M. A. Shtern, and G. D. Suslova, Tekhnol. Svoistva Miner. Pigmentov,
1971, 35 (Chem. A h . , 1973,78,51 962h).
1114 M. Azzopardi, A. Galerie, and J. Besson, Bull. SOC.chim. France, 1972, 3684.
l1lS J. B. Homer and A . Prothero, J.C.S. Faraday I , 1973, 673.
1116 M. J. Shea and W. C. Michels, J . Chem. Phys., 1973, 59,2764.
1117 W. Jeitschko and A. W. Sleight, Actu Cryst., 1972, B28,3174.
1118 D. J. Steward, 0. Knop, R. E. Meads, and W. G. Parker, Canad. J . Chem., 1973,51,
1041.
lllD P. Panek and R. Hoppe, 2. anorg. Chem., 1973,400,219.
1120 G . M. Smirnova, A. B. Zdanovskii, S. G . Sushkova, T. N. Zhitkova, I. A. Leont'eva,
and Z. I. Shishkina, Rum. J . Inorg. Chem., 1973,18,271.
llZ1 K. Hardel and B. Strocka, 2. phys. Chem. (Frankfurt), 1973, 83,234.
1123 G. M. H. van de Velde, U. Spitsbergen, and P. J. Gellings, J . Inorg. Nuclear Chem.,
1973,35,675.
llZ3J. C. Ruckman, R. T. W. Morrison, and R. H . Buck,J.C.S. Dalton, 1972,426.
1111
1112
410
groups eclipsed to within 11 f 5" The Pb2f ions are irregularly co-ordinated
by 8 or 9 oxygen atoms, with lead-oxygen bond distances ranging from 2.40
to 3.20A?124
The structure of tin(@ sulphate consists of a framework of sulphate groups
linked by 0-Sn-0
bridges. The tin(rr) atoms have typical pyramidal coordination with Sn-0 bond distances of 2.25-2.27A and LOSnO =
77.1-79.0' (Figure 42).1125In the thiourea complex SnS04,2(H,N),CS, the
0 0
Figure 42 Structure of SnSO,

tin atoms are in distorted pyramidal sites surrounded by two sulphate oxygen
atoms at 2.41 and 2.24A, and by two thiourea sulphur atoms at 2.62 and
2.56A. The planar, but inequivalent, thiourea groups are linked to the
sulphate ions by hydrogen-bonding (Figure 43).1126The structure of the basic
tin(@ sulphate Sn,0(OH2)S0, is shown in Figure 44. The three tin atoms
form a triangle, with one oxygen atom co-ordinated to all three tin atoms. The
two hydroxide ions are each co-ordinated to two tin atoms. On the third side
of the Sn, triangle, a sulphate oxygen atom bridges two tin atoms. Thus, two
of the tin atoms are three-co-ordinated and the third is four-co-ordinated by
oxygen atoms. The tin triangles form a zigzag chain running along the b-axis.
That the two hydroxide groups have different modes of co-ordination is
demonstrated by d.t.a., which indicates that water is expelled in two steps
that are separated by 65 O C , and by the 0-0 distances (2.61, 2.68, and
2.79A)?l2' The only isolable phases from the aqueous K-Sn'I-SO, and
K-SnIT-SO4-X (X = F, Cl, Br, I, or NO3) systems were potassium tin(r1)
sulphate, of composition ranging from K2Sn(S0& to K,Sn,(SO,),, and
llZ6
R. D. Shannon and C. Calvo, Canad. J. Cliem., 1973,51,70.

J. D.Donaldson and D. C. Puxley, Acta Cryst., 1972,B28, 864.
J. D.Donaldson, D. G. Nicholson, D. C. Puxley, and R. A. Howie, J.C.S. Dalton,
112'
S.Grimvall, Actu Chem. Scund., 1973, 27, 1447.
llZ5
1973, 1810.
41 1
BE\:
Figure 43 Structure of SnS0,,2(H2N),CS

Sn
0'
Figure 44 Structure of Sn,O(OH),SO,

(Reproduced by permission from Actu Chem. Scand., 1973,27, 1447)
412
potassium tin(r1) chloride and bromide sulphates, K3Sn2(S04),X.The former

are essentially similar to chloro-apatites, with SO2- replacing PO3- 112*A
procedure for the synthesis of l13SnS04has been reported.l12@
The crystal structure of dihydrogen ethylenediaminetetra-acetat ostannate(I1)
is shown in Figure 45. The tin atom is centred in the rectangular face of a
Figure 45 Structure of dihydrogen ethylenediaminetetra-acetatostannate(11)

(Reproduced from J.C.S. Dalton, 1973,741)
distorted triangular prism, co-ordinated by two nitrogen atoms at 2.338 and

2.442A and by four oxygen atoms at 2.196, 2.343, 2.635, and 3.057A.
Intermolecular hydrogen-bonding links carboxy-groups from adjacent
The effect of 7-irradiation
molecules, forming a one-dimensional p01ymer.l~~~
on the thermal decomposition of lead formate (to give PbO, formaldehyde,
and CO,) at around 200 O C has been studied?l3l Anhydrous lead citrate may
A. Howie, W. Moser, R. G. Starks, F. W. D. Woodhams, and W. Parker, J.C.S.
Dalton, 1973, 1478.
R.A. Hiles, J . Labelled Compounds, 1973, 9, 87.
K. G. Shields, R. C. Seccombe, and C. H. L. Kennard, J.C.S. Dalton, 1973, 741.
M. N. Ray and N. D. Sinnarkar, J. Znorg. Nuclear Chem., 1973,35,1373.
lla* R.
112s
1130
1131
Eiements of Group IV
413
be prepared by the dehydration of the tetrahydrate or the dihydrate, but the
products appear to be structurally different. The thermal decomposition of
both types has been studied.1132The rates of complexation of lead(rr) carboxylates with piperidine have been investigated.1133Thevibrational spectra of
the peroxylead compound of composition 2PbC,O6,5PbO,CO2(or 2PbC,O,,PbC03,4Pb0) show that the active oxygen is bound as peroxy-dicarbonate,lla
Tin([[) dimethoxide,diacetate, bis(oximes), bis(hydroxylamines), dicyanide,
and derivatives of 1,2- and 1,3-diazoles and 1,2,4-triazoIe have been synthesized by the protolysis of the tin(Ir)-carbon bonds of cyclopentadienyl compounds. (C,H,)(CO)3WH also reacted to form a Sn-W bonded derivative.l135
Tin(rr) bis-(l,3-diketonates) may be prepared similarly, or by the substitution
of tin(@ chloride by the sodium 1,3-diketonate. These compounds undergo
exchange with SnCI, to form tin([[) chloride mono-l,3-diketonates, and
oxidative addition with methyl iodide to afford methyliodotin(rv) bis-(l,3diket~nates).ll,~
The dehydration of hydrated lead oxynitrate, Pb(N03),,2PbO,+H,O, has been studied by d.t.a.113' The thermodynamics of the hydrolysis
of secondary lead orthophosphate, PbHPO,, have been studied. Values of
AG: for PbHPO,, and for Pb3(P04),, Pb,(PO,),OH, and Pb40(PO4), were
calculated to be -281.8, -565.0, -902.0, and -617.3 kcal mol-l, respect i ~ e l y . 1 ~ ~ ~
Compounds containing Siiicon(1r)-, Germanium(r1)-, Tin@)-, and Lead(11)Chaicogenide Bonds. Solid SiS has been prepared in an amorphous form by
condensing gaseous SiS at high temperatures. The solid is metastable and
disproportionates into SiSz and sulphur at an appreciable rate above 950 K.
SiS appears to be thermodynamically unstable below 1452 K. Vaporization
of SiSz yields predominantly SiS and S2. Thermodynamic properties of SiS
have also been evaluated.1139 The reaction of GeS with aqueous KOH gives
initially Ge(OH),, which is then converted into K,Ge0,.1140 The protolysis of
tin(I1)-carbon bonds by thiols yields tin([[) dithiolates Sn(SR),. Sn(SMe), is
unstable, forming SnS and Me$ even at room temperature.1141 In aikinite,
PbCuBiS,, the lead atom is co-ordinated by five sulphur atoms at distances
ranging from 2.84 to 2.98 A in locations close to an octahedral environment ;
two additional sulphur neighbours are located at 3.24 A (Figure 46).llg2The
crystal structures of both bis(NN-diethy1carbamato)-tin(@ and -lead(Ir) have
1132
1133
1134
1135
1136
113'
1138
113B
11*0
1141
1142
M. E. Brown, J.C.S. Faraday Z, 1973, 1202.

R. I. Kharitonova and S. S. Sydykova, Zhur.$z. Khim., 1973, 47, 892.
M. Manewa, nlonatsh., 1973, 104, 742.
P. G. Harrison and S. R. Stobart, J.C.S. Dalton, 1973, 940.
K. D. Bos, H. A. Budding, E. J. Bulten, and J. G . Noltes, Inorg. Nuclear Chem.
Letters, 1973, 9, 961.
J. J. P. Martin, C. Martin-Lefevre, and E. Husson, Bull. SOC.
J. A . Nriagu, Znorg. Chem., 1972, 11, 2499.
J. J. Byerley and W. K. Teo, J . Inorg. Nuclear Chem., 1973, 35, 2195.
V. P. Kindeeva and T. N. Komarova, Zzvest. Nauch. -Issled. Inst. Nefte-Uglekhim.
Sin. Zrkutsk. Univ., 1969, 11, 106 (Chem. Abs., 1973,78, 11 060f).
P. G. Harrison and S. R. Stobart, Inorg. Chim. Acta, 1973, 7, 306.
I. Kohatsu and B. J. Wuensch, Acta Cryst., 1971, B27, 1245.
414

S ( 2 ' ) 3-28a
S(3') 2.95A
A
S(1") 2.98w
Figure 46 Co-ordinationpolyhedron of the lead in PbCuBiSs

been determined. Both contain discrete M(S,CNEt,), molecules, with both

groups functioning as bidentate ligands towards the metal atoms, which enjoy
a distorted pyramidal configuration. The structure of the tin compound is
shown in Figure 47. Each dithiocarbamate group forms one short (2.574,
2.592 A) and one long (2.765, 2.819 A) bond.11g3The structure of the lead
compound is depicted in Figure 48. Again the dithiocarbamate ligands are
The crystal
anisobidentate; r(Pb-S) = 2.744,2.786 A and 2.885,2.950
structure of the very similar lead@) diethyldithiophosphate Pb [S2P(OEt)212
also consists of monomeric units, in which the lead atom is again in distorted
L
Figure 47 Structure of Sn(S,CNEt,),
(Reproduced by permission from Acta Cryst, 1973, B29, 1830)
1143
lla4
J. Potenza and D. Mastropaolo, Acta Cryst., 1973, B29, 1830.

H. Iwasaki and H. Hagihara, Acta Cryst., 1972, B28, 507.
a
41 5
I
Figure 48 Structure ofPb(S,CNEt,),

pyramidal co-ordination. The Pb-S bond distances range from 2.75 to
3.022 A (Figure 49).1145
All three compounds possess a stereochemically
active lone pair of electrons. Herbstein has determined the structures of four
lead carboxylate-thiourea complexes. The first co-ordination sphere of Pb'I in
Pb(HC02),,2tu,H20 (tu = thiourea) has three sulphur and five oxygen atoms
in a distorted dodecahedra1arrangement. Two parallel - - - S - - - Pb - - - S
chains extend along [OOl], with each pair of centrosymmetrically related lead
ions bridged by two similarly related formate ions. The sulphur atoms of the
thiourea molecules are bico-ordinated, whilst each bridging formate ion has
one unico-ordinate and one bico-ordinate oxygen atom. The remaining
1145
T. Ito, Acta Cryst., 1972, B28, 1034.
416

thiourea molecule, water molecule, and formate ion are unico-ordinatively
bonded to the same lead ion (Figure
Pt(tu),(ClO,), contains rather
closely packed [Pb(tu)J2f cations and Cl0;r anions. The cation has six-fold
co-ordination of sulphur atoms about lead in a distorted octahedral arrangement [all r(Pb-S) = 3.06 f 0.01 A, but the SPbS bond angles lie in the
range 79-100')
(Figure 51).l14' The structure of Pb(tu),(picrate), contains
Figure 49 Structure of Pb[S,P(OEt),],

polymeric chains of edge-sharing distorted Pb(tu), octahedra (Figure 52)

and stacks of picrate ions. The crystal is made up of interleaved parallel
cationic and anionic sheets, with interconnecting hydrogen-bonding. The
distances from lead to shared sulphur atoms range from 2.87 to 3.23 A, and
to unshared sulphur atoms they are 2.96 A>148
Eight-co-ordination of Pb" is
found in $Pb(HCO2),,4(tu). The lead is surrounded by twisted tetragonal
prisms of sulphur atoms of thiourea molecules (Figure 53). Every fourth
lead position is vacant, the vacancies being fully ordered. The Pb-S bond
distances range from 2.98 to 3.85 A.1149The Pb-S distances in all complexes
correspond to ion-dipole interactions.
The kinetics of the oxidation of SnTe115*and PbTe1151have been studied.
At temperatures of 200-300 "C,the SnTe lattice parameters decrease from
I. Goldberger and F. H. Herbstein, Actu Cryst., 1973,B29,246.
I. Goldberger and F. Herbstein, Actu Cryst., 1972,B28,400.
1148 F. H. Herbstein and M. Kaftony, Acra Cryst., 1972,B28,405.
114B I. Goldberg and F. H. Herbstein, Acta Cryst., 1972,328,410.
1160 M. I. Parshina, L. A. Firsanova, Yu. A. Beilin, and 0. P. Obukhova, Termoelek.
Mater., 1971,45 (Chem. Abs., 1973,78, 51 956j).
nS10. P. Obukhova, L. A. Firsanova, Yu. A. Beilin, and M. I. Parshina, Termoelek.
Muter., 1971,51 (Chem. Abs., 1973,78,48476~).
1146
417
Figure 50 Structure ofPb(HCO,>,,2(H2N)ZCS,H20

6.32 to 6.30 A owing to the dissolution of oxygen. At 400 'C,SnO, and TeO,
start to form, and at 600 "C SnTe20, appears in the reaction products. PbTe
absorbs oxygen at low temperatures, and this is followed by the formation
of PbO and PbTeO, at 450C. PbOd is formed at 50O0C, and PbTeO,
and PbTeO, at 600C. At higher temperatures, PbTeO, and PbTeO, decompose.
Lea~(I1)PseudohdZides.
The crystal structure of the complex Pb(SCN),,C,2H2sN,O, shows that the lead ion lies in the plane of the four oxygen atoms, the
two nitrogen atoms being on both sides. The co-ordination sphere of the lead
is completed by the sulphur atoms of the NCS ions, one above and one below
the ring. The lead thus has hexagonal-bipyramidal co-ordination. The
418
"4)
Figure 51 Structure of the {Pb[(H,N)3CS]6}u- cation in [Pb(tu),]C10,

Pb-N and P b - 0 bonds are essentiallyelectrostatic, whereas the Pb-S bonds
are covalent in character. The Pb-S, Pb-0, and Pb-N bond distances
are 2.894, 2.897, and 2.787 and 2.751 A, re~pective1y.l~~~
The effect of particle
size on the thermal decompo~ition,ll~~
the photodecomposition and electronic
s t r ~ c t u r e and
~ ~ ~the
* i.r. spectra1lS5of d e a d azide have been studied.
Organometallic Derivatives of Bivalent Germanium, Tin, and Lead. The
oxagermacyclopentanes RHGeO(CH,), (R = H or C1) decompose by (xelimination with the formation of the 7-hydroxy bivalent germanium species
RGe(CH,),OH, which can insert into alkyl halides, alkyl-lithiums, and
GeC1,.1156 Curtis has synthesized (C5H5)2Geby the reaction of sodium or
t hallium(1) cyclopentadienide with freshly prepared GeBr,. Polymerization
to polymeric [(C5H5),Ge], is complete in ca. three
The treatment of
the disodium salts of 7,s- and 7,9-B,HgCHE2- (E = P or As) with Ge12 in
refluxing benzene results in the formation of 1,2,3- and 1,2,7-GeB,H,CHE
icosahedral boranes. The proposed structure for the lY2,3-isomeris shown in
1153
1153
llK6
1156
115'
B. Metz and R. Weiss, Act0 Cryst., 1973, B29, 1088.

R.W. Hutchinson, S. Kleinberg, and F. P. Stein, J . Phys. Chem., 1973,77, 870.
R. B. Halland F. Williams, J . Phys. Chem., 1973, 58, 1036.
S. P. Varma and F. Williams, J . Chem. Phys., 1973,59,912.
J. Barrau, J. Satge, and M. Massol, Helv. Chim. A m , 1973, 56, 1638.
J. V. Scibelli and M. D. Curtis, J. Amer. Chem. SOC.,1973, 95, 924.
419
Figure 52 The polymeric chain of edge-sharing octahedra in Pb(tu),(picrate),

28
420
0SH
8 CH
Figure 54 Proposed structure for 1,2,3-GeB,H9CHE (E = P or As). The

germanium atom may be slpped toward boron atoms 4, 7, and 8 .
(Reproduced by permission from J. Organometallic Chem., 1973,50,93)
421
Figure 54. Heating 1 ,2,7-GzB9H,CHP at 512 "Cfor 8 h in an evacuated sealed
tube yields a mixture of three
Tin(@ chloride reacts with
(Me,Si),CHLi in ether at 0 O C to give the red crystalline, monomeric, diamagnetic Sn[CH(SiMe3),l2. This compound may function as a Lewis base
{displacing CO from M(CO), (M = Cr or Mo) to form [(Me,Si),CH],Sn --j.
M(CO)S complexes) and as a Lewis acid (reacting with y-picoline to give
[(Me,Si),CHI2Sn +- NC,H,Me). The analogous lead compound has also
been prepared.1159The structure of the unusual compound Bu$nCr(CO),,py
is shown in Figure 55. The Cr(CO), residue has virtual C,, symmetry.
Figure 55 Structure of Bu$hCr(CO),,py

(Reproduced by permission from J. Amer. Chern. Soc., 1973,95,4529)
The Bu$n group is bonded to the chromium atom [r(Sn-Cr) = 2.654 A],
and the pyridine is co-ordinated to the tin atom [r(Sn-N) = 2.29 A]. The
Sn-C bonds are relatively long (2.24, 2.25 A). The bond angles at
tin show that the arrangement is intermediate between tetrahedral and
trigonal-bipyramidal.Ileo (MeC,H,),Sn forms a 1 :1 complex with AlCl,.1161
Complexation Behaviour of Lead(@ in Aqueous Media. The complexation of
lead(@ in mixed halide (CI, Br) and perchlorate solutions of constant ionic
strength has been studied. The equilibria occurring can be described by four
lead chloride and five lead bromide mononuclear c o m p l e ~ e sComplex
.~~~~~~~~
D.C. Beer and L. J. Todd, J . Organometallic Chem., 1973, 50,93.
P. J. Davidson and M. F. Lappert, J.C.S.Chem. Comm., 1973, 317.
llS0M. D.Brice and F. A . Cotton, J . Amer. Chem. SOC.,1973,95,4529.
1161 J. Doe, S. Borkett, and P. G. Harrison, J . Organometallic Chem., 1973,52, 343.
llS2F. Vierling, Bull. SOC.chim. France, 1972,4096.
116s F . Vierling, Ann. Chim. (France), 1973, 53.
115*
1159
422
formation between PbT1 and citrate ions in both acid116*and alkaline1165

solution ; dipicolinic acid in aqueous 0.5M-NaCI0,;1166 trans-cyclohexane1,2-diaminetetra-aceticacid in DMF ;1167polyglycine peptides;*168propylene1,3-diaminetetra-acetic acid and ethylene-NN'-diacetic-NN'-dipropionic
acid;116Qethy1enediamine;ll7Oand threonine in water, water-DMF, and
~ a t e r - D M S 0 . l The
~ ~ ~hydrolysis of lead(I1) in aqueous solution has been
studied electrophoreticallyand tyndall~rnetrically.~~~~
The electrode reduction
of lead rnalate,l17, and the effects of the surfactants I-menthol, &camphor,
and thymol on the faradaic reduction of lead(11)ll~~
have been studied. The
activity coefficients of mixed lead(@ and zinc nitrates in aqueous solution at
25 *C have been calculated.1175 Mixing an alkaline solution of 2,4,6-trinitroresorcinol (H,L) with aqueous Pb(NO,), or Pb(ClO,), produces
a-Pb(OH),L at pH = 5-9, and Pb,(OH),,L, at pH = 10-12.5, and two
metastable s01ids.l~~~
Catalytic Activity of Silicon- and Tin-containing Systems.-The low-temperature (<lSO"C) oxidation of carbon monoxide on catalysts obtained by
thermal activation of grannular hydrous tin(1v) oxide gel in the range 200500 "C has been investigated. From a study of the kinetics of the steady-state
reaction at 180-210 'C, a mechanism was proposed which involves adsorption of CO, desorption of C02, and oxygen regeneration of the ~ a t a 1 y s t . l ~ ~ ~
Coprecipitated Sn02-CuO gels, particularly those having a Cu :Sn atomic
ratio of between 0.5: 1 and 0.6: 1, are even better catalysts, and function at
temperatures < 100 0C.1178Several studies of alkene oxidation over mixed
tin-molybdenum and tin-antimony oxide systems have been reported. The
route of oxygen incorporation into oxidized products has been studied in the
heterogeneous oxidation of propene by molecular oxygen over a Sn0,-Moo,
catalyst in the presence of [lsO]H,O tracer. l 8 0 Tracer is incorporated into
the acetone produced, but not into the simultaneously produced acrolein.
Thus there appear to be two different active species of oxygen on the catalyst
surface, one derived from water and the other from molecular oxygen.
Oxidation to acetone depends on the interaction with water-derived active
species, while oxidation to acrolein depends on a species derived from molecular oxygen. The mechanism of acetone formation seems to involve the
E. Bottari and M. Vicedomi, J . Znorg. Nuclear Chem., 1973,35, 1269.
E. Bottari and M. Vicedomi, J . Znorg. Nuclear Chem., 1973, 35, 2447.
L. Campanella, G. de Angelis, and A. Napoli, Bull. SOC.chim. belges, 1972, 81,489.
1167 S. K. Dhar and D. A. Stroz, Inorg. Nuclear Chem. Leffers,1972, 8, 1019.
116* D. L. Rabenstein and S. Libich, Znorg. Chem., 1972, 11,2960.
1168 B. J. Fuhr and D. L. Rabenstein, Inorg. Chem., 1973, 12, 1868.
1170 K. Zwetanov, A. Tonev, and K. Kantshev, Monatsh., 1973, 103,496.
1171 P. C. Rawat and C. M. Gupta, Indian J. Chem., 1973, 11, 186.
1172 B. Pokrici and Z . Pucar, J . Inorg. Nuclear Chem., 1973, 35, 1987.
1173 S. C. Khurana and C. M. Gupta, Austral. J. Chem., 1973, 26,971.
1174 S. La1 and G. D. Christian, Monatsh., 1973, 104, 1214.
1175 G. A. Motornaya and E. Ya. Benyash, Rum. J . Znorg. CJtem., 1973, 47, 260.
1'0
A. Durtschi and W. Rauber, Helv. Chim. Acta, 1973, 56,644.
117' M. J. Fuller and M. E. Warwick, J. Caralysis, 1973, 29,441.
117* M. J. Fuller and M. E. Warwick, J.C.S. Chem. Comm., 1973,210.
1164
1165
423
surface reaction between a carbonium ion and the active species of water to
form an alcoholic intermediate.1179The amount of acidic sites, determined by
n-butylamine titration, correlates with the catalytic activity to form acetone;
the activity increases with the surface concentration of acidic sites on the
Sn0,-MOO, catalyst.llsODeuterium substitution of propene has also been
investigated. CH,=CHCH, reacts ca. 2.2 times faster than CH,=CDCH,.
In a series of runs involving the four combinations of CH,=CHCH,,
CD,=CHCD,, H,O, and D20, introduction of deuterium into the propene
produced no change in the collective rate of formation of acetone, acetic
acid, and acetaldehyde, but the rate decreases upon a change-over from H 2 0
to D20, suggesting that propene is chemisorbed as isopropyl groups. No
kinetic isotope effect is observed in the formation of acrolein from [2-2H]propene, but one was observed with propene deuteriated in the methyl and
methylene positions, again demonstrating separate mechanisms for the
formation of acetone, acetic acid, and acetaldehyde on the one hand, and
for acrolein.llsl
The oxidation of propene to acrolein and the ammoxidation of propene to
acrylonitrile over SnO,, Sb,03, and the five mixed oxides of the Sn-Sb-0
system have been studied. The physical and catalytic properties of these
systems change with composition and temperature of thermal treatment
(460-950 "C in air). The tin-rich Sn-Sb-0 oxides show a single-phase solid
solution of Sb203 in SnO,, with a SnO, structure, which reaches a
maximum antimony concentration at the composition Sb/Sn = &.The initial
selectivities of the catalysts in the range of the saturated solid solution
(Sb/Sn > Q) are virtually independent of composition and of temperature of
treatment (750-950 "C), and about 90 % and 80 % respective conversions of
propene into acrolein and acrylonitrile are achieved. SnO, has a high activity,
but a low selectivity, while Sb,O, is highly selective, but has a low activity.lls2
The Sn-Sb-Fe-0 catalyst shows high selectivity (92 %), but the maximum
for the conversion of propene into aldehyde does not exceed 41 % for a 60 %
transformation of the hydrocarbon. The other products are oxides of carbon
and very small amounts of ethylene and a~eta1dehyde.l~~~
The isotopic exchange reaction of MeOH, containing a PtII-SnI' chloride
complex, with D, in the temperature range 0-20 O C and up to 100 Torr is
first-order in deuterium. The rate exhibits a maximum at a Sn/Pt ratio of 5.5,
lending support to the idea that the active catalyst is Pt11(SnCl,)t.1184 The
catalytic efficiencies of SnX, (X = C1 or Br) and PhSnC1, in the racemization
of a-methylbenzyl chloride in ether have been studied. For all catalysts, the
reaction is first-order in alkyl halide, but a mixture of first- and second-order
1179
1180
Y.Moro-okayY.Takita, and A. Ozaki, J . Catalysis, 1972,27, 177.

Y. Takita, A. Ozaki, and Y . Moro-okayJ. Catabsis, 1972, 27, 185.
Buiten, J . Catalysis, 1972,27, 232.

M. Crozat and J. E. Germain, Bull. SOC.chim. France, 1973, 1125.
1lSs M. Crozat and J. E. Germain, Bull. SOC.chim. France, 1973, 2498.
m4 K.Hirabayashi and I. Yasumori, J.C.S. Faruday I , 1973, 595.
llS1 J.
llS2

for SnX, and a mixture of first- and third-order for PhSnX3. The first-order
catalytic rate constants are in the order SnCl, > SnBr, > PhSnC1,.1185
NN'-Tetrakis (trimethylsily1)cobalt diamine, Co "(SiMe,), J2, effectively catalyses the trimerization of allenes at room ternperature.llss
424
Miscellaneous Physical Measurements.-In this section are included physical

data not previously mentioned. Binding energies of silicon, germanium, tin,
and lead compounds have been determined by X-ray photoelectron spectroscopy.1187J188The enthalpies of formation of several trimethyl-silyl, -germyl,
Table 41 Enthalpies of formation and bond energieslkcalmol-l
AH;
Compound
(Me,Si),O (1)
Me3SiC1(1)
Me,SiOEt (1)
(Me,Ge),O (1)
Me,GeCl (1)
Me,GeBr (1)
Me,GeOEt (1)
Me3GeSBun(1)
Me,GeNMe, (1)
Me,SnOH (c)
Me,SnCl (c)
Me,SnBr (c)
Me,SnI (I)
Me,SnOEt (1)
Me3SnSBun(1)
Me,SnNMe, (1)
(Me,Sn),NMe (1)
(Me,Sn),N (c)
-AHoas (c or 1)
- -194.7
-91.8
5.7
-126.4
-136.0
1.7
0.5
6.9
-1.1
25.8
3.3
2.4
4.2
18.3
5.1
38.2
43.6
70.2
-71.6
-62.1
-95.8
-64.7
-37.1
-90.8
-58.4
-48.8
-31.2
-73.1
-47.1
- 13.3
-31.5
-29.2
Bond
AHvap
8.9
7.2
8
9
8
9
8
10
8
15
12
14
11.5
10
10
9
12
15
-185.8
-84.6
-118.4
-127.0
-63.6
-53.1
-87.8
-54.7
-29.1
-75.8
-46.4
-34.8
-19.7
-63.1
-37.1
-4.3
-19.5
-14.2
105
96
103
82
81
68
79
58
55
77
75
61
45
66
52
41
48
42
Si-0
Si-Cl
Si-0
Ge-0
Ge-CI
Ge-Br
Ge-0
Ge-S
Ge-N
Sn-0
Sn-Cl
Sn-Br
Sn-I
Sn-0
Sn-S
Sn-N
Sn-N
Sn-N
and -stannyl compounds have been deduced from their heats of hydrolysis in
aqueous 1M-hydrochloric acid, and the relevant thermochemical bond energies E(M-X) evaluated. These data are listed in Table 4l.llsS
Intermetallic Phases.-Binary Systems. Although a vast number of papers
describing the results of research into intermetallic phases are published
annually, all but a few are of little direct interest to the inorganic chemist.
The structural properties of a number of binary intermetallics including a
R. M. Evans and R. S. Satchell, J.C.S. Perkin II, 1973, 642.
J. Furukawa, J. Kiji and K. Ueo, Makromol. Chem., 1973, 170,247.
1187 W. E. Morgan and J. R. van Wazer, J. Phys. Chem., 1973,77,964.
1188 P. A. Grutsch, M. V. Zeller, and T . P. Fehlner, Inorg. Chem., 1973, 12, 1431.
1189 J. C. Baldwin, M. F. Lappert, J. B. Pedley, and J. S. PolandJ. C. S. Dalton, 1972,1943
1185
1186
425
Group IV element have been investigated;1190-1198 the phases described will
be considered in order of increasing content of the Group IV element. An
X-ray investigation of the effect of high pressures and temperatures on the
structure of Mg2Sn, which under normal conditions has the antifluorite
structure, has been carried
At pressures greater than 30 kbar (at
25 "C) and 40 kbar (at 400 "C), a high-pressure phase, which exists as a
metastable phase under normal conditions, has been found to be formed.
It is hexagonal, a = 13.12 f 0.02, c = 6.99 f 0.04A;a model is proposed
for the structure which is similar to that of the Ni2Si structure type. A
single-crystal X-ray diffraction study of K - F ~ , G
has
~~
shown it to crystallize
with monoclinic symmetry, space group C2/m, with a = 9.965, b = 7.826,
c = 7.801 A, and /3 = 109O 4O'.llg1 The magnetic properties of this phase and
those of the monoclinic form of FeGe have been found to be very similar;llD2
they are both antiferromagnetic with N k l temperatures of 336 f 2 and
345 f 2 K, respectively. They also exhibit an unexplained magnetic transition
at ca. 110 K. An X-ray diffraction and calorimetric investigation of Cu,Sn5
has confirmed11g3that the phase transformation occurring at ca. 460 K is of
the type:
simple superlattice q (high temp.)
+long-period superlattice 7' (low temp.)
The crystal structures of PtSi and PtGe have been determined;llg4 the
compounds are isostructural with MnP, space group Pbnm, PtSi having the
slightly smaller unit cell (Table 42). The i.r. spectra of the Sif and GetTable 42 Lattice parameters/A of PtSi and PtGe
a
b
c
PtSi
PtGe
5.916
6.084
5.577
3.587
5.719
3.697
anions, previously proved by X-ray studies to be tetrahedral, have been

determined in the compounds Na,Si,, K,Si,, Rb,Si4, Cs,Si,, Ba,Si4, and
K4Geq.llg5The F2 fundamental of the tetrahedron, which according to the
space group Pa3n-Ti is split into 2 or 3 components, was observed in the
K, Rb, and Cs compounds. From the i.r. wavenumbers of -345cm-1
(Sif-) and -195 cm-l (Gef), the smallest ground-state stretching forceconstants of Si-Si (-1.05 mdyn A-l) and Ge-Ge bonds (-0.87 mdyn
llBo
T.I. Dyuzheva, S. S. Kabalkina, and L. F. Vereshchagin, Soviet Phys. Cryst., 1973,
llB1
llBa
llB3
lIg4
llg5
llg6
lIg7
llS8
B. Malaman, A. Courtois, J. Protas, and B. Roques, Compt. rend., 1973,276, C , 665.

B. Malaman, A. Courtois, J. Protas, and B. Roques, Compt. rend., 1973,276, By 323.
17, 705.
A. Gangulee, G. C. Das, and M. B. Bever, Metallurg. Truns., 1972,3, 2063.

E. J. Graeber, R. J. Baughman, and B. Morosin, Acta Cryst., 1973, B29, 1991.
H. Burger and R. Eujen, Z . anorg. Chem., 1972, 394,19.
G. Zwilling and H. Nowotny, Monatsh., 1973,104,668.
K. Miller and H. T. Hall, Inorg. Chem., 1972,11, 1188.
A. Percheron, 0.Goruchov, and J . 4 . Achard, Compt. rend., 1973, 277, C , 81.
426
A-l) so far known were obtained. The crystal structure of the defect silicide
MnSi,-, (n = 0.25-0.30) has been determined and its stoicheiometry defined
as Mn27Si,7.1196New LnSn, compounds of face-centred cubic structure
(AuCu, type) have been prepared11g7for Tb, Dy, Ho, Er, and Y (Table 43)
under high pressures (85 kbar) and temperatures (1400"C);analogous
compounds have not been observed in the Lu-Sn and Sc-Sn systems. The
magnetic susceptibility and electrical resistivity of the compound EuSn,
have been determined as a function of temperature (10-300 K).llg8 The
Table 43 Lizttice parameters/A of LnSn, compounds
a
Compound
TbSn,
DySn,
HoSn,
ErSn,
YSn,
4.661
4.659
4.653
4.648
4.666
f 0.002
f 0.001
f 0.001
f 0.002
f 0.002
measurements indicate that at temperatures below 38 K the sample exhibits

ant iferromagnetism.
The presence of an ordered structure in the solid solution Fe-18 atom % Ge
has been confirmed by electron microdiffraction and Mossbauer spectroscopy.1199The short-range order in the Ag-Si liquid eutectic alloy has been
investigated by X-ray diffraction techniques at 840,850, 870, and 890 oC.1200
The experimental data were found to be consistent with atomic radialdistribution curves calculated on the assumption of a completely random
distribution of atoms of different kinds in the liquid.
Phase equilibria in the Au-Pb,1201 Mg-Sn,1202 and A1-Si1203 systems have
been investigated. The Au-Pb phase diagram has been established1201 by
d.t.a., d.d.t.a., X-ray metallography, and microhardness measurements on
twenty samples. The existence of a new non-congruent compound AuPb, is
shown, as well as the instability of Au,Pb at low temperature (< 247 "C).
The hypoeutectic tin-rich liquidus of the Mg-Sn system has been measured;1202
the eutectic temperature was established as 201.5 f 1 O C at 2 atom% Mg.
Approximate thermodynamic calculations based on regular solutions have
been used to determine the lines of the phase equilibria in the AI-Si system at
pressures of 0, 10,25, and 50 kbar.1203With increasing pressure the eutectic
composition changes in the direction of Si, and the temperature of the
eutectic equilibrium rises.
lls9
lZoo
L. Rimlinger and C. Lecorre, Compt. rend., 1973, 216, C , 735.

Ya. I. Dutchak, V. S. Frenchko, and V. M. Klanichka, Russ. J . Phys. Chem., 1973,47,
415.
1201
lZo2
lzo3
B. Legendre and C. Souleau, Bull. SOC.chim. France, 1973,2202.

J. Ellmer, K. E. Hall, R. W. Kamphefner, J. F. Pfeifer, V. Stamboni, and C. D.
Graham, Metallurg. Trans., 1973, 4, 889.
A. Ya. Shinyaev, D. B. Chernov, and G. I. Khokhlova, Russ. J . Inorg. Chem., 1972,
46, 1667.
Elemenrs of Group IV
427
Values of the integral enthalpy of mixing in the Ga-Sn and In-Sn binary
systems have been determined by quantitative d.t.a.lZo4The maximum values
of the enthalpy of mixing in the two systems are +214 f 6 cal (g atom)-l
(Ga-Sn) and -72 f 2 cal (g atom)-l (In-Sn). The enthalpies of solution of
Dy,lZo5Er,lZo5and Eu1206in liquid tin have been measured at 957, 963, and
957 K, respectively. The partial molar enthalpies of solution at infinite
dilution obtained from these results are collated in Table 44.The heat of
Table 44 Partial molar enthalpies of solution of Dy, Er, and Eu

in tin at infinite dilution
System
Ap"O/kcal(g atom)-l
Ref.
Dy-Sn
Er-Sn
-36.44
Eu-Sn
-42.61
1205
1205
1206
-29.25
solution of the compound EuSn, has also been determined, from which the
enthalpy of formation of EuSn, has been calculated to be AHo (EuSn,) =
-50.48 kcal mol-l.
Thermodynamic properties of liquid Mn-Si,1207Fe-Sn,1208and Ga-Pbl2O9
solutions have been determined over the entire composition ranges; thermodynamic properties of dilute solutions of Cu and Sb in liquid tin1210and of Cd
in liquid lead1211have also been measured.
Ternary Systems. The crystal structures of several ternary systems containing
at least one Group IV element have been e l ~ c i d a t e d ; ~ ~that
~ ~ of
- l EuMg,~~~
Ge,1212has been shown to be orthorhombic, of space group Cmcm, a = 4.485,
b = 30.60, c = 4.485 %., and is thought to belong to a new type derived from
1204
1206
1206
la07
1208
1209
1210
iaii
1212
1213
1214
1216
A. S. Skoropanov, L. A. Mezakovskii, D. M. Zakarov, and A. A. Vecher, Russ. J.

Phys. Chem., 1973, 47,426.
A. Bacha, C. Chatillon-Colinet, A. Percheron, and J.-C. Mathieu, Compt. rend.,
1972,275, C , 921.
A. Bacha, C. Chatillon-Colinet, A. Percheron, J.-C. Mathieu, and J.-C. Achard,
Compt. rend., 1973,276, C , 995.
M. S . Petrushevskii, P. V. Kucherov, P. V. Gel'd, V. M. Zamyatin, and S. 1. Suchil'
nikov, Russ. J. Phys. Chem., 1973, 47, 158.
S. Wagner and G. R. St. Pierre, Metallurg. Trans., 1972,3,2873.
A. Desideri and V. Piacente, J. Chem. and Eng. Data, 1973, 18,90.
D. A. Griffiths, J. Braithwaite, L. W. Beckstead, and G. R. B. Elliott, J. Electrochem.
SOC.,1973, 120,301.
Z. Moser, K. Fitznor, and L. Zabdyr, Rev. Roumaine Chim., 1973, 18,557.
0. F. Zmii, E. I. Gladyshevskii, and V. S. Bul'o, Soviet Phys. Cryst., 1973, 18, 171.
0. I. Bodak, E. I. Gladyshevskii, and M. G. Mis'kiv, Soviet Phys. Cryst., 1972, 17,
439.
K. P. Mukerjee and K. P. Gupta, Metallurg. Trans., 1973, 4, 618.
A. A. Frolov, F. A. Sidorenko, R. P. Kreutsis, and P. V. Gel'd, Russ. J. Inorg. Chem.,

1972, 17, 1347.
1216
1217
1218
121s
M. D. Lind and R. W. Grant, J. Chem. Phys., 1973,58, 357.

S . P. Vul' and T. V. Pakhomova, Soviet Phys. Cryst., 1973, 17, 1110.
M.Guigueno, J. Guyader, and J. Lang, Compt. rertd., 1973,276, C, 351.
D. M. Freik, V. V. Voitkov, G. M. Gaiduchuk, and I. I. Brodin, Soviet Phys. Cryst.,
1973, 17,964.
428
the AIB,, CeMg,Si,, and CaF, types. The crystal structure of Ce,NiSi is
also of a new type;1213it is hexagonal, of space group P6,/n, and is a derivative
of the Rh,Sil, structural type. The distribution of the Ni and Si atoms in the
compound which has a variable composition Ce,Nio~8-l~2Sil,2,~8is partially
disordered. The existence of the isostructural compounds La2NiSi and
Pr,NiSi has also been established (Table 45).1213Evidence for a MgZn,-type
Table 45 Lattice pararneters/A ofLn,NiSi (Ln = Ce, La, or Pr)
Compound
Ce2NiSi
La,NiSi
Pr,NiSi
16.12
16.34
16.05
4.309
4.322
4.302
Laves phase in the Mn-Cu-Si system has been obtained;1214 the exact
location of the Laves-phase region, however, has not been fully documented.
The symmetry of the phase is hexagonal, a = 4.830, c = 7.834 A. The limits
of mutual solubility of Fe2Siand Ni,Si at 1373 K have been measured and the
concentration dependencies of the lattice parameters of the solid solutions
have been found.1216The replacement of Fe atoms by Ni atoms in Fe,Si gives
rise to trigonal distortion of the cubic cell (a = 2.81 A for Fe,Si)J215 Precise
structural data have been recorded for the two hexagonal chalcopyrite
structures ZnGePz and ZnSiAs,1216 (Table 46). The structural dependence of
Table 46 Lattice parameters of ZnGeP, and ZnSiAs,
Compound:
Space group:
ZnGePI
142d
alA
5.46 f 0.01
10.71 f 0.01
CIA
ZnSiAs,
142d
5.60 f 0.01
10.88 f 0.01
birefringence in the chalcopyrite structure has also been assessed for these
compounds and other more well-known chalcopyrites. A new selective etchant
for the chalcopyrite CdSnAs, composed of 30 % H,02 (one part by volume),
40% HF (one part) and H20 (four parts) has been described;l2I7the etching
time is 5-11 minutes at room temperature.
The two ternary phases Cal,Si,As16 and Ca,SiAs, have been prepared in
the system Ca-Si-As.1218 X-Ray diffraction analysis has shown Cal,Si,Asl,
to crystallize with monoclinic symmetry, a = 7.134(5), b = 17.651(10),
c = 7.267(5) A,
= 111.7(5)', and Ca,SiAs, with cubic symmetry, Q =
12.171(4)A. The preparative techniques and several of the properties of the
ternary products are described in detail.
The results of a study of the dependence of the structure of thin layers of
(SnTe),,(PbSe),
and (SnTe),,(PbTe),
on the phase composition (0 <
x Q 1) have shown the existence of a continuous series of solid solutions with
the rock-salt structure in both systems?219The composition dependenceof the
crystal lattice parameters of the solutions was in accord with Vegard's law.
429
Phase relationships in the systems Au-Te-Sn,l"O Mo-Ti-Si,1221 and
In-Ga-Sn1222 have been investigated. That part of the Au-Te-Sn ternary
phase diagram along the two invariant tie lines, AuSn-SnTe and AuTe,SnTe, between the three congruently melting compounds has been determined.1220Although the AuTe,-SnTe system is a simple eutectic (32.5 mole %
SnTe, 402 "C) the AuSn-SnTe system is somewhat more complex, exhibiting
a monotectic (25-88 mole % SnTe, 750 "C)as well as a eutectic (1.3 mole %
SnTe, 413 "C).The MoSi,-TiSi, phase diagram has been established by
metallographic X-ray diffraction and high-temperature d.t.a. techniques.1221
A ternary phase with hexagonal structure of the CrSi, typ-e, a = 4.674(5),
c = 6.502(5)& has been found to exist over the homogeneity range 26-86
mole % MoSi, (at 1425 "C)and 35-85 mole % MoSi, (at 1300 "C); it was
established that the ternary phase is a high-temperature modification of
MoSi, stabilized by titanium. In a calorimetric study of eutectic In-Ga-Sn
alloys,1222the ternary eutectic has been established at 20.5 wt.% In, 67
wt.% Ga, and 12.5 wt.% Sn, temperature 10.4 f 0.1 OC. Measurement of
the integral enthalpy of mixing in this system has also been effected by
quantitative d.t.a.; the results are presented as contour lines of equal entha1~y.l~~~
Thermodynamic studies of the two ternary systems Ag-Pb-Sn1224 and
c ~ - S b - S n lhave
~ ~ ~been carried out in the liquid phase. The former system1224
has been studied at fixed Pb :Ag ratios (3 :7, 1 :1, and 7 :3) over the entire tin
composition range. The latter system1225has been studied at high tin concentrations only (>86 atom% Sn). The effects of liquid structuring are
discussed in relation to the solution activity equations, and it is also
concluded that solute-solute interactions between antimony and copper have
little effect on the tin activity.
lZ2O
1221
1222
1223
lZz4
1225
B. Legendre, C. Souleau, and J.-C. Rouland, Compt. rend., 1972,275, C , 805.

V. N. Svechnikov, Yu. A. Kocherzhinskii, and L. M. Yupko, Doklady Chem., 1973,
206, 756.
L. S. Topchyan, D. M. Zacharov, R. B. Lyudviov, and M. I. Druelashvili, Russ. J .
Phys. Chem., 1973,47, 158.
A. S. Skoropanov, L. A. Mechkouskii, D. M. Zakarov, and A. A. Vecher, Rum. J .
Phys. Chem., 1973, 47,426.
K. P. Jagannathan and A. Ghosh, Metallurg. Trans., 1973, 4, 1577.
D. A. Griffiths, J. Braithwaite, L. W. Beckstead, and G. R. B. Elliott, J. Electrochem.
Soc., 1973, 120, 301.
Elements of Group V
~~
BY A. MORRIS AND D. B. SOWERBY
1 Nitrogen
Elementary Nitrogen.-Far-infrared evidence has been presented to confirm
that the space group of cc-N, is P2,3. As well as the k = 0 translational lattice
mode at 49 cm-l there are two bands, at 38 and 58 cm-l, closely coincident
in energy with the Raman lines at 36.5 f 2 and 60 f 2 cm-l, which have been
assigned as three-fold degenerate k = 0 librational lattice modes. Such a
coincidence is forbidden by the mutual-exclusion rule for centric groups.
Thus, previous investigations assuming the space group Pa3 must be reconsidered. A linear spin-wave theory has been used to calculate the frequencies of librational modes in the a phase of nitrogen2and the form of the
intermolecular potential considered. The shape of the vibrational Raman
band of N, dissolved in various solvents has been compared3 with the one
obtained from N, gas. For N, in SF, the rotational correlation function has
been analysed.
ESCA studies of dinitrogen continue to appear. It has been pointed out,
however, that the nitrogen molecule is one of the simplest examples where
Koopmans theorem not only fails in predicting accurate values for the
vertical ionization potentials but even yields the wrong sequence of the two
lowest ionization^.^ The problem was only resolved by recourse to a very
elaborate form of perturbation theory. The 304 A [He(II) radiation] photoelectron spectrum of N, has been recorded using radiation dispersed with a
grazing-incidence mono~hromator.~
Transitions to electronic states with
ionization potentials in the range 3 0 4 0 . 8 eV were shown to be dissociative,
and preliminary branching ratios for transitions to all the electronic states
appearing in the 304A spectrum have been given. In the 11.8-13.8eV
range: differential-threshold and energy-loss spectra have been obtained at
a,
E. J. Wachtel, J. Chem. Phys., 1972, 57, 5620.

P. V. Dunmore, J. Chem. Phys., 1972,57, 3348.
Y. Le Duff, J. Chem. Phys., 1973,59, 1984.
L. S. Cederbaum, G. Hohlneicher, and W. Von Niesson, Chem. Phys. Letters, 1973,
18, 503.
J. L. Gardner and J. A. R. Samson, J. Electron Spectroscopy, 1973,2,259.
G . Joyez, R. 1. Hall, and J. Mazeau, J. Electron Spectroscopy, 1973,2,183.
430
Elements of Group V
43 1
an incident energy of 14.3 eV. The study of the angular behaviour permitted
a distinction to be made between singlet-singlet and singlet-triplet transitions. For the first time? Rydberg series of vibrationally excited states of
N2 converging to the A2n,and B 2 C i limits are reported. Also, completely
new data on the doubly excited levels of N, have been observed. Calculations
of core binding energies (extended Huckel wavefunctions) in nitrogencontaining compounds give a poor fit with experimental N 1s shifts.8
The equations-of-motion method has been very successful in calculating
excited statesg and potential-energy curves1* for the dinitrogen molecule. A
more empirical approach, using Raman spectra of a-N2,suggests that a better
fit is obtainedll for n = 9 than the previously used n = 12 for P.E. curves.
Dinitrogen complexes of transition metals have been reviewed, appropriately, by A. D. Allen and co-workers.12It was emphasized that although
most chemists assume that dinitrogen complexes of transition metals are
involved, at some stage, in the biological fixation of dinitrogen, no fully
characterized dinitrogen complex has been reduced to ammonia. However,
the compounds are of considerable intrinsic interest. Recent developments
have centred on model systems for nitrogen reduction and simple complexes
containing only N, as a ligand. In the former systems, Russian workers have
concentrated on the reduction of nitrogen to hydrazine. Three papers have
appeared. In the first13 an unstable complex (Cp2Ti),N,MgC1 (isolated at
-60 "C) was reported, which formed N,H, when treated with methanolic
HCl. The other two papersl4nl5presented work on the multicomponent
system: Zn-N2-V11-V'11-Mg'1-Zn'1-KBr-KOH-H,0.It was found that
the yield of hydrazine was a function of the concentrations of all
the reagents in the system and the temperature. A correlation was found
between the yield of hydrazine and the redox potential of the system. Also,
an increase in the MgII concentration led to a rise in the yield of N,H, and a
shift in the redox potential to the anodic region, whereas an increase in the
ZnII concentration led to a fall in the yield of N,H4, and the redox potential
shifted towards the cathodic region. Schrauzer, on the other hand, has used
nitrogenase model systems, composed of molybdate-L( +)-cysteine complexes
as catalysts, in the reduction of various nitrogen-containing species to ammonia, with NaBH, as the reductant. This system reduces aliphatic nitriles
'
R. Carbonneau and P. Marmet, Internat. J. Mass Spectrometry Ion Phys., 1972, 10,
143.
M. E. Schwartz and J. D. Switalski, J. Amer. Chem. Soc,, 1972, 94,6298.

J. Rose, T. Shibuya, and V. McKay, J . Chem. Phys., 1973, 58,74.
l o W. Coughran, J. Rose, T. Shibuya, and V. McKay, J . Chem. Phys., 1973, 5 8 , 2699.
l1 N. Jacobi and 0. Schnepp, J. Chem. Phys., 1973,58, 3647.
l2 A. D. Allen, R. 0. Harris, B. R. Leoscher, J. R. Stevens, and R. N. Whiteley, Chem.
Rev., 1973, 11, 73.
l3 Yu. G. Borodko, I. N. Ivleva, L. M. Kachapina, E. F. Kvashina, A. K. Shilova, and
A. E. Shilov, J.C.S. Chem. Comm., 1973, 169.
l4 D. V. Sokol'skii, Ya. A. Dorfman, Yu. M. Shindler, S. S. Stroganov, and A. N.
Sharopin, J. Gen. Chem. (U.S.S.R.).,1973,43,252.
l5 D. V. Sokol'skii, Ya. A. Dorfman, Yu. M. Shindler, B. Yu. Nogerbekov, and R. G.
Sapova, J. Gen. Chem. (U.S.S.R.).,
1972,42,1415.
432
to NH, and alkanes.18 The catalytic process involves co-ordination of the
nitrile to the molybdenum, and the role of ATP in the complexation reaction
has been elucidated. All previously observed reactions of nitriles with nitrogenase are essentially duplicated by the model systems and thus nitrile binding and reduction by nitrogenase must occur at the molybdenum active site
of the Fe-Mo-protein. Iron appears to function mainly as an activator of
electron transport to the molybdenum site. The principal reduction products
of other nitrogen species1' are summarized in the equations (1)-(4). Fixation
N,CHCO,Et + CHSCOpEt
N
2
(4)
of nitrogen has been shown to be molybdenum-specific by the use of 15N2,

and the effect of ATP has been investigated in detail.
The mode of co-ordination of the N, ligand in NiN, has been determined
by an elegant isotopic labelling technique18 to be in an 'end-on fashion'.
Table 1 shows the four wavenumbers predicted by this geometry for the four
Table 1 Calculated and observed wavenumberslcm-l for linear NimNnN,
where m,n = 14, I5
Observed
2020.6
2053.6
2057.4
2089.9
Calculated
2019.7
2053.6
2057.4
2090.6
Assignment
NPN,
NP4NlSN
Nil6Nl4N
Nil",
possibilities NirnNnN(where M ,n = 14, 15). It was suggested that the metalnitrogen bonding is similar in chemisorbed N, on Ni. Analogous matrixisolation experiments provided unambiguous evidencel9that N, is bonded in a
'sideways' fashion to cobalt in CoN2. In an extensive piece of work20 the
products of cocondensation of Ni and Pd atoms with N, in low-temperature
(4.2-10 K) matrices have been shown, by a combination of i.r. and Raman
spectroscopy, to be Ni(N2), and Pd(N,), (n = 1 - 4 and rn = 1-3), respectively. It is somewhat surprising that Pd is co-ordinativelysaturated at Pd(N,),
N. Schrauzer, P. A. Doemeny, R. H. Frazier jun., and G. W. Kiefer, J. Arner.
Chem. SOC.,1972, 94,7318.
G. N. Schrauzer, G. W. Kiefer, P. A. Doemeny, and H. Kisch, 3. Amer. Chem. SOC.,
l6
G.
1'
1973,95, 5582.
M . Moskovits and G. A. Ozin,J. Chern. Phys., 1973, 58, 1251.

Is G. A, Ozin and A. Vander Voet, Canad. J . Chem., 1973, 51, 637.
ao H. Huber, E. P. Kiindig, M. Moskovits, and G. A. Ozin, J . Amer. Chem. Soc., 1973,
l*
95, 332.
Elements of Group V
433
when Ni(N,), is readily formed in the nickel system. In all cases the M-N-N
bonding is linear and the symmetries of the species are: Ni(N,), and Pd(N,),,
Dab; Ni(N2), and Pd(N2),, D,; and Ni(N2)4, Td.Two reports of Pt(N,),
complexes have appeared. In one,21 x values of 1 , 2, and 3 were claimed,
whereas no complex Pt(N,), was mentioned by the other workers.22Also,
there is disagreement on the frequency assignment and geometry of Pt(N,),.
The first examples of transition-metal complexes containing both N, and
O2co-ordinated to the same metal have been reported.23Detection was by
matrix-isolation i.r. spectroscopy and the structures suggested are as shown
in (1) and (2).
It is convenient to mention here a critical review2*of the structure determination of nitrogen compounds with the aid of n.q.r., n.m.r., and ESCA
spectroscopy. Ab initio calculations have been carried out for a number of
compounds containing nitrogen.25In particular, the effect of the lone pair on
geometric and electronic structure predictions was studied and compared
with the available experimental evidence.
Bonds to Hydrogen.-From a consideration of recent X-ray diffraction studies
on inorganic complexes it has been concluded26that, in general, hydrogen
atoms fixed in calculated positions with N-H = 0.87 A provides the best
description of the electron density distribution.
15N-lH n.m.r. coupling constants have been determined2 for fourteen
amino-phosphines, amino-phosphoranes, amino-arsines, sulphenamides,
and amino-silanes. The results were explicable in terms of the redistribution
of electrons without invoking a n-bonding model in the N-P compounds.
NH and NH2 Compounds. The electronic structures of singlet and triplet

states of the nitrenium ions NH;, NHFf, and N q have been studied using
ab initio techniques.28 It was found that although fluorine substitution
destabilizes both the singlet and triplet states, the triplets are destabilized to a
greater extent, Energy-localized orbitals have been generated from INDO
wavefunctions for the r-radicals NH,, N(CH,),, NC2H4,and NH: to test the
23
24
ab
as
E. P. Kundig, M. Moskovits, and G. A. Ozin, Canad. J. Chem., 1973, 51, 2710.

D. W. Green, J. Thomas, and D. M. Gruen, J . Chem. Phys., 1973,58,5453.
W. E. Klotzbucher and G. A. Ozin, J . Amer. Chem. SOC.,1973, 95, 3790.
H. G. Fritzby, D. Wendisch, and R. Holm, Angew. Chem. Internat. Edn., 1972, 11,
979.
D. W. Geuson and R. E. Christoffersen,J. Amer. Chem. Soc., 1972, 94,6904.
M. R. Churchill, Inorg. Chem., 1973, 12, 1213.
A. H. Cowley and J. R. Schweiger, J. Amer. Chern. SOC.,1973, 95,4179.
J. F. Harrison and C. W. Eakers, J . Amer. Chem. SOC.,1973,95, 3467.

currently used model for r-0 orbital polari~ation?~
Ab initio SCF and CI
calculations of the reaction surface for the reaction:
434
indicate that the reaction is best described in terms of two distinct potential
curves: one attractive, representing the formation of a CN bond; the other
repulsive, characterizing the interaction between nitrogen non-bonding
electrons and the olefinic centre.30
Gas-phase nucleophilicities of the ions H-, F,OH-, and NH; have been
estimated31from a consideration of the kinetics of the reaction :
X-
+ CHaCl = CHaX + C1-
(where X- = H-, F-, OH-, or NH;). It was concluded that the order of
nucleophilic reactivity is H- > NH; M OH- M F-.
Useful thermochemical data have been derived32 from a study of the
proton- transfer reaction :
cm3
The rate constants were found to be kforward
= (2.3 f 0.5) x
molecule-l s-l and kTeVerSd
= (9.2 f 1.8) x
cm3molecule-l s-l. The
ratio of the rate constants kf/kr = 2 6 ( + 6 , -5) was found to be in good
agreement with the equilibrium constant, K = 27 f 9, derived from equilibrium concentrations. The following quantities are some of the more
important ones which were derived: AG& = -1.9 f 0.2 kcal mol-l;
D ; ( N H , - - H ) = 1 0 6 . 0 f 1.1 kcalmol-l; Di,,(NH,--H)
= 107.4 f 1.1 kcal
mol-l, and AH;,,,,(NH,) = 44.3 f 1.1 kcal mol-l.
Further spectroscopic evidence33 confirms the presence of NH in the
stratosphere.
NH, and Derivatives. As part of a systematicstudy of properties and functions
of catalysts for ammonia synthesis, correlations have been sought3*between
the promoter addition procedure and the physicochemical properties and
activity of catalysts obtained by the fusion of natural magnetite. The results
show that the manner of addition of the promoter affects, to a large extent,
the investigated properties and catalyst activity.
Two papers have discussed the formation of atmospheric aerosols from the
NH,-SO,-H,O-air
gas-phase reaction. Previous theories have concentrated on the possibilities of chemical reaction in pre-existing droplets or on
30
K. F. Purcell and W. C. Danen, J . Amer. Chem. SOC.,1972,94,7613.

S. Shih, R. J. Buenker, S. D. Peyerimhoff, and C. J. Michejda, J. Amer. Chem.
SOC.,1972,94,7620.
L. B. Young, E. Lee-Ruff, and D. K.Bohme, J.C.S. Chem. Comm.,1973,35.

D. K. Bohme, R. S. Hemsworth, and H. W. Rundle, J. Chem. Phys., 1973,59,77.
ss R. W. Nicholls, Nature Phys. Sci., 1972, 240, 142.
B. D. Aleksic and A. Terlecki-Baricevic, Rev. Roumaine Chim., 1973, 18, 575.
3a
Elements of Group V
435
the role of chemical reactions preceding the phase transition. A new
focusses attention on nucleation, using a modified form of the authors
theory of heteromolecular nucleation. NH,,S02 was postulated as an intermediate in the formulation of NH,S04 and it was concluded that water
vapour plays an extremely important role in that it can change the rate of
nucleation by orders of magnitude at varying relative humidities less than
100%.The observed36rates of particle formation agree well with the predictions based on the above model, but the large increase in rate with increase in relative humidity was not observed. However, the discrepancy
may be due to the large size of the measured particles. Heicklen has initiated
a series of studies on the kinetics of particle growth. This year he and his
co-workers have looked at the formation of ammonium nitrate from the
ammonia-ozone reaction37and the kinetics of the reaction of ammonia with
hydrogen chloride and the growth of particulate ammonium chlorideF8
With increasing concern about pollution in urban areas the number of such
studies may well increase in the future.
A steady-state flow apparatus has been used to determine39the pressure
dependence of the relative quasi-bimolecular rate constants for the reactant
pairs NH, + Me,N and Me,HN
Me,N in their reaction with BF3. The
reactions between NH, and the amalgams of Mn, U, Ti, and A1 produce
Mn,HgN, UN1.,,, TiN, and AlN, respe~tively.~~
Orders of reaction were
determined for the above cases but for Fe and Cr, which have very low
solubility in Hg, reaction was so slow that no reaction products could be
isolated or identified. An in~estigation~l
of the photolysis of NH, and ND,
has revealed an important isotope effect. The ratio of molecular and atomic
hydrogen produced by photolysis at 147 and 123.6 nm was +=J+H > +D,/#D
while at 185 nm +Hz/+H = +D,/+D. The dissociation:
NHs
+ hv
4 NH
+H +H
occurs at wavelengths as high as 147 nm, implying that D(NH-H)

mol-l. Also, the rate constant for the reaction:
D
+ ND3
4 Dz
< 90 kcal
+ ND2
is kD+NDF = 3.5 x 1013exp( -14 400/RT)cm3mol-l s-l.

Quantized rotational motion had only been observed previously for HCl,
was made of NH, dissolved in liquid SF,;
HF, and DCl until a
3G
36
37
38
38
*O
41
4a
29
C. S. Kiang, D. Stauffer, and V. A. Mohnen, Nature Phys. Sci.,1973,244,53.

A. Arrowsmith, A. B. Hedley, and J. M. Beer, Nature Phys. Sci., 1973, 244, 105.
R. G. de Pena, K. Olszyna, and J. Heicklen, J. Phys. Chem., 1973, 77,438.
R. J. Countess and J. Heicklen, J. Phys. Chem., 1973, 77,444.
S. Glicker, J . Phys. Chem., 1973,77, 1093.
P. Ettmayer and G. Jangg, Monatsh., 1973, 104, 1120.
J. Masanet, J. Fournier, and C. Vermeil, Cunad. J. Chem., 1973, 51,2946.
G. Birnbaum, Mol. Phys., 1973, 25, 241.

resolved rotational structure was observed in the far4.r. regions. The controversy whether or not ammonia rotates in nitrogen and argon matrices continues. An investigation4, of the temperature dependence of the lines in the v2
region has been explained in terms of rotation of molecular NH, in argon but
not in nitrogen matrices. Matrix-isolation techniques have been used to
investigate two other systems. The i.r. spectra of the 1 :1 adduct of NH, and
HCl, and of the various isotopically substituted deuterio-analogues, have
been obtained44in nitrogen matrices at 15 K. A strong hydrogen bond is
formed involving specifically the hydrogen atom of the HCl molecule which
is shared nearly equally between the chlorine and nitrogen atoms. Thus, the
hydrogen atoms of the complex are not equivalent. The i.r. spectra of BH,NH,, BD3-ND3, and BH,-ND, have been measured in argon matrices at
liquid-helium temperatures;45all the fundamentals were assigned and force
fields computed.
A reinterpretation4* of molecular beam hyperfine data for 14NH3 and
15NH, has led to reassignments for the hyperfine patterns of six 15NH3
inversion doublets. As a result, the sign of the nitrogen-hydrogen spin-spin
interaction constant has been altered. Calculation of the potential barrier to
inversion of NH, using the SCF X a SW method has been reported?' The
results depend heavily on the choice of sphere radii owing to the way the
total energy was computed.
The electron spectra of the 2Al+- lA1 and the 2Ec lAl transitions of NH,
have been measured48with sufficient resolution to observe considerable fine
structure. The first transition, 2A, f- lA,, contains two vibrational progressions which are assigned to the v2 bending mode. The second transition,
2E+ lA,, consists of two overlapping electron bands owing to the JahnTeller splitting of the 2E state, The vibronic structure accompanying this
transition has been partially resolved and compared with the results of model
calculations. The electron-impact-inducedionization and dissociation of NH,
have been studied by quadrupole mass s p e c t r ~ m e t r yDeconvoluted
.~~
firstdifferential ionization-efficiencycurves were presented and a comparison was
made with the corresponding photoionization and photoelectron spectra.
INDO MO theory has been used50 to show that lJ(15N, H) and 2J(HNH)
in NH, are very sensitive to the HNH angle in the range 110-120". The
computed trends were compared with those observed in other compounds
containing the l5NH, grouping.
436
43
44
46
46
41
48
49
6o
J. A. Cugley and A. D. E. Pullin, Spectrochim. Acta., 1973,29A, 1665.

B. S . Ault and G. C. Pimentel, J. Phys. Chem., 1973,77, 1649.
J. Smith, K. S. Seshadri, and D. White, J . Mol. Spectroscopy, 1973, 45, 327.
J. T. Hougen, J. Chem. Phys. 1972, 57,4207.
U. Wahlgren, Chem. Phys. Letters, 1973,20,247.
J. W. Rabalais, L. Karisson, L. 0. Werme, T. Bermark, and K. Siegbahn, J. Chem.
Phys., 1973, 58, 3370.
J. D. Morrison and J. G. Traeger, Internat. J. Mass Spectrometry Ion Phys., 1973,11,
277.
R. E. Wasylishen and T. Schaefer, Canad.J . Chem., 1973, 51,3087.
Elements of Grot;p V
437
Studies on liquid ammonia have been concentrated in two fields :vibrational spectroscopy and electrical conductivity investigations. In an extensive
piece of workS1Hester and co-workers have reported the Raman spectra of
liquid ammonia and of NH3dissolved in carbon tetrachloride and acetonitrile
(covering a wide concentration range). In the pure liquid, association between
NH, molecules was observed and in acetonitrile there are ammonia-solvent
interactions. However, in dilute CCI, solutionsessentiallyfree rotation of NH,
molecules was indicated in the spectra. Previous uncertainty about the assignment of bands in the N-H stretching multiplet of the liquid ammonia
spectrum was removed. Lagowski et al. have measured the Raman spectra
of NH,, ND,, and ND,H and of solutions of NaI and NaClO, in liquid
ammonia at various temperature^.^^ A two-species model for the solvent
structure was suggested from the resolution of the experimental envelopes in
the N-H and N-D stretching regions. The band positions for the pure
liquids and solutions were discussed in terms of the proposed structure. A
third reporP3 of the Raman spectrum of liquid ammonia observed that the
v2 band was split into a doublet. Also, in the same article, studies were made
of alkali metal-ammonia solutions in the concentration range 0-50 x
lo4 moll-l. No scattering centre attributable to the solvated electron was
found, nor were the positions of the bands altered by the presence of the
solute in the concentration range used. The intensity of the scattered radiation
was found to decrease with increasing metal concentration and was attributed
to the absorbance of these solutions. Rather different conclusions about the
nature of lithium and potassium solutions in ammonia were derived from i.r.
~pectra.5~
The N-H stretching frequency shifted to lower energy with increasing metal concentration and the shift was independent of the metal over
the concentration range 5 x
to 5 x
moll-l. The results were
interpreted in terms of the formation of new solvent-containing species in the
presence of solvated electrons. The solvent in these species is polarized
primarily by the electron; the weakening of the N-H bond was attributed to
the increased electron density on solvent molecules associated with the solvated electron and from co-ordination by cations present in the systems.
Finally, vibrational spectra of LiN03 and NH4N03in liquid ammonia have
been measured over a wide concentration range.55Large changes in the N-H
stretching region were correlated with the effects of the electrolytes on the
solvent structure and low-frequencybands were assigned to Li-NH, modes.
Both solvent-separated and contact ion pairs involving Li+ and NO; were
indicated but contact ion pairing between NHf and NO; produced no
measurable splitting of the E' modes of NO;.
61
D. J. Gardiner, R. E. Hester, and W. E. L. Grossman, J. Raman Spectroscopy, 1973,
69
1,87.
A. T. Lemley, J. H. Roberts, K. R. Plowman, and J. J. Lagowski, J . Phys. Chem.,
1973,77,2185.
53
54
66
B. L. Smith and W. H. Koehler, J. Phys. Chern., 1973, 77, 1753.

P. F. Rusch and J. J. Lagowski, J . Phys. Chem., 1973, 77,210.
D. J. Gardiner, R. E. Hester, and W. E. L. Grossman, J . Chem. Phys., 1973,59, 175.
Inorganic Chemistry of the Muingroup Elements
438
Gill and Lowe66have used previously reported activity-coefficient measurements to calculate ion-pair and triple-ion formation constants (KA and KT)
for NH4N03and NH41in liquid ammonia at -40 "C. For NH4N03, K A =
401 =t 9 dm3mol-l and KT = 11.4 f 0.7 dm3 mol-l, and for NHJ, KA =
476 f 20 dm3 mol-l and KT = 6.5 f 0.8 dm3mol-l, when the size parameter
in the Debye-Huckel equation is set at the Bjerrum critical distance (16.22 x
10-lom). As a result of their analysis, revised activity coefficients were
calculated. A detailed analysis has been made of the kinetics of the hydrogen
electrode reaction in liquid ammonia at low temperatures6' to ascertain its
suitability as a reference electrode. The reaction was shown to be less reversible than in aqueous media and this was attributed to inhibition by materials
adsorbed on the platinum surface which arise from the decomposition of the
solvent. The conductivities of hexamminecalcium ( K = 10-l l2-l cm-l 1,
calcium amide, and amidoethoxycalcium ( K = lob6 52-1 cm-l) have been
measureds8 in liquid ammonia. By measurement of the conductivities of the
reaction solutions the conversion of Ca(NH,);+ into Ca(NH& and
Ca(NH,)OEt in the presence of ethylene oxide was investigated.
Two studies have been carried out on the NH,-HF system in the concentration range 78-83 % HF between 19 and 34 "C. Measurements of the
density and viscosityss and the electrical conductivity60suggest that the ions
NHZ and F- are solvated in solution.
More complete measurements of the density and viscosity of ND, have been
reported61over the range +30 to -25C. At any given temperature PNDJ
pNH3 = 1.187 rt 0,001 and qND3/qNHII
= 1.20 f 0.01, suggesting that the
strengths of the intermolecular interactions are essentially the same in the
two liquids and the differencein the density and viscosity are attributable to
differences in molecular size and mass. Using the spin-echo technique,
measurements of the self-diffusion of neat NH, and ND3 (between 200 and
298 K) may be represented by
D = (4.5 f 0.2) x 10, exp[-(2.07 f 0.02)/RT]
D = (6.0 f 0.3) x 1O3exp[-(2.31 f 0.02)/RT]
and
for NH3 and ND,, respectively.s2

Calculations on hydrogen-bonded systems involving ammonia continue to
calculate different, but similar,
appear. Two studies of the NH3,H20
binding energies using different methods of calculation. In a related series of
J. B. Gill and B. M. Lowe, J.C.S. Dalton, 1972, 1959.
0. R. Brown and S. A. Thornton, J.C.S. Furuduy I , 1973, 69, 1568.
V. N. Epimakhov, M. M. Tarnorutskii, Yu. M. Mishenov, and N. B. Kolosova,
1973, 43, 502.
K g F. Breda and M. Rolin, Bull. SOC.chim. France, 1972, 3733.
6o G. Pourcelly and M. Rolin, Bull. SOC.chim. France, 1972, 3738.
61 M. Alei jun., and W. M. Litchman, J . Chem. Phys., 1972, 57,4106.
62 D. E. O'Reilly, E. M. Peterson, and C. E. Scheie, J . Chem. Phys., 1973,58,4072.
63 A. Meunier, B. Levy, and G. Berthier, Theor. Chim. Actu, 1973, 29, 49.
84 G. H. F. Diercksen, W. P. Kraemer, and W. von Niessen, Theor. Chim. Acta, 1973,
66
67
29, 49.
Elements of Group V
439
dimers ROH,NH, (where R = H, CH,, NH,, OH, or F), equilibrium
structures and energies have been c a l c ~ l a t e d .Proton
~~
transfer has been
analysed6ein the complex [H3N-H,NH3]+, and the solvent effect on the
reaction :
NH,
HF = NH4F
has been computed by an ab initio MO calculati0n.~7

Aqueous Curl and (edta)Ferr efficientlycatalyse the oxidation of hydroxylamine to nitrogen by hexacyanoferrate(II1). A mechanism involving association between the catalyst and an intermediate N H 2 0 was proposed; pentacyanoferrates and other secondary reaction products have no significant
catalytic activity.68
Ab initio restricted SCF calculationseghave elucidated a non-least-motion
rearrangement path for the interconversion of H,NO to the stable H2NOH
that bears some resemblance to the allowed motion of 1,3-sigmatropic shifts.
The stability of the observed F3N0 relative to the unknown FzNOF was
discussed.
From the molar excess enthalpy of the system carbon tetrachloridetriethylamine (measured at 298.15 K) it was concluded that complex formation occurred, with the CCI, acting as a Lewis acid and Et,N as a Lewis
base.70A comprehensive study71of the i.r. and Raman spectra of the C2H0]to [2H,]-trimethylaminesin the solid state at - 180 OC has allowed a complete
assignment to be made. Identification of magnesium-ligand stretchings in the
complexes MgX,(CH,),N (X = C1, Br, or I) and MgBr,(CD,),N was thus
facilitated and the shifts in the donor vibrations were discussed. In the series
(CH,),M (M = N, P, CH, or SiH) for the amine, phosphine, and silane the
theoretical minimum of energy calculated by the CND0/2 approach72is in
agreement with the available experimental data, i.e. the so-called LEM conformation in which each methyl group is staggered with respect to the two
opposite M-C bonds. Isobutene is predicted to have the same conformation.
When methylamine is allowed to react with hydrogen atoms the stable
products are H,, NH,, CH,, and C2Hg,in the temperature range 473-683 K.
However, e.s.r. and molecular beam sampling techniques have allowed the
rate constant for the reaction:
H
+ CHSNHZ + CNHd + HZ
J. E. Del Bene, J. Amer. Chem. SOC.,1973, 95, 5460.

P. Merlet, S. D. Peyerimhoff, and R. J. Buenker, J. Amer. Chem. SOC.,1972, 94,
8301.
6 7 S. Yamabe, S. Kato, H. Fujimoto, and K. Fukui, Theor. Chim. Acta, 1973, 30, 327.
6 8 G. J. Bridgart, W. A. Water, and I. R. Wilson, J.C.S. Dalton, 1973, 1582.
6Q C. Trindle and D. D. Shillady, J . Amer. Chem. SOC.,1973, 95, 703.
7 0 D. V. Fenby, Austral. 5. Chem., 1973, 26, 1143.
71 J. Kress and J. Guillermet, J. Chim. phys., 1973, 70, 374.
7 3 M. Corosine, F. Crasnier, M.-C. Labarre, J.-F. Labarre, and C. Leibovia, Chem.
P h p . Letters, 1973, 20, 111.
ct5
66
440
to be evaluated. CH, and NH2 radicals appear as intermediate^.'^ N.m.r.

studies of a,p, and y phases of solid CH3NH,CI (and its partially deuteriated
analogues CD,NH,Cl and CH,ND,Cl) have led to resolution of the motions
in these phases.74
NHZ Compounds.By analogy with the corresponding sodium compound, for
which a crystal structure is available, it has been claimed that [Co(salen>l2,NH4SCN,THF is the first compound in which NHZ is complexed to a coordination c0mpound.7~
The ammonium halides are well known to undergo a number of structural
modifications with temperature. Four phases occur at atmospheric pressure;
in phases I and I1 the NHZ ions are disordered and in phases I11 and IV they
'
. A
are ordered. The 'disorder-order' transition temperature is designated 7
number of studies have appeared in which these phenomena have been probed,
principally by single-crystal Raman spectroscopy. Orientation relations have
been reported76for the transformation of NH,Br from phase I (NaCl type)
to phase I1 (CsCl type). The observations indicated a displacive mechanism
which rotates the [lll] direction; this could be common in these lattices.
Wang and Wright have studied the Raman spectra of NH4C177and NH4Br,78
analysing spectral bandwidths, intensities, and frequencies as a function of
temperature. For NH4Cl new results were reported for both sides of 7'~
and an
examination of the polarization properties of various spectral components
suggested that well-defined Raman selection rules are operative in the disordered crystal. In the work on the bromide a single-domain NH4Br single
crystal was used and the librational motion below Tk investigated. The
correlation time and spectral linewidth versus temperature data both showed
an Arrhenius type of temperature dependence, which was attributed to the
thermally induced hydrogen-bond-breaking process. This work was extended
to cover the disordered phases I and I1 of NH,CI, NH4Br, and NH41.70
Further work on phase I NH41 has been interpreted by introducing the
missing translational invariance of a disordered crystal into the second-order
perturbation theory of the Raman effect.*O In high-pressure studies, transitions involving a phase V were investigated, again by Raman spectroscopy.8'
Finally, a normal-co-ordinate treatment of the optically active lattice vibrations of NH4Cl and ND4Cl at low temperature was made in order to
elucidate the nature of the vibrations and obtain force constants in the potential in the
Using the force constants, the optically active lattice
73
B. Blumenberg and H. Gg. Wagner, Ber. Bunsengesellschaft phys. Chem., 1973, 77,
74
253.
S. Albert and J. A. Ripmeester, J. Chem. Phys., 1973, 58, 541.
76
76
?'
78
70
**
8a
C. Floriani, F. Calderazzo, and L. Randaccio, J.C.S. Chem. Comm., 1973, 384.

W. L. Fraser and S. W. Kennedy, Acta Cryst., 1972, B28, 3101.
C. H. Wang and R. B. Wright, J. Chern. P h p . , 1973,58, 1411.
C. H. Wang and R. B. Wright, J. C h e w Phys., 1973, 58,2934.
M. Couzi, J. B. Sokoloff,and C. H. Perry, J . Chem. Phys., 1973,58,2965.
W. Dult and H. Ihlefeld, J. Chem. Phys., 1973, 58, 3365.
Y . Ebisuzaki, Chem. Phys. Letters, 1973, 19, 503.
K. Fukushima and H. Yamamoto, Bull. Chem. SOC.Japan, 1972,45,3058.
Elements of Group V
441
vibrations of a crystal model of NH,Cl and ND,Cl at room temperature were
calculated.
Dilatometry has been used to study the phase change:
NH,NO,(III)
+ NH,NO,(IV)
from both direction^.^, In this way the transition temperature was found to be
32.1 'C. High-resolution 15Nn.m.r. spectra have been obtained in the solid
state, by the transfer of polarization from protons, for (NH4),S0,, NH4N03,
and g l y ~ i n eA. ~new
~ double salt of composition (NHJ2SiF6,NH4NO3belongs
to the hexagonal crystal system.86
The thermal decomposition of ammonium salts is an important field of
study. Kinetic parameters for the decomposition of NH,N03 have been
determined,86it being found that the addition of small amounts of NH4C1
reduces both the thermal stability and the initial decomposition temperature
of the nitrate. Confirmation of a previously proposed mechanism for the
chloride-transition-metal-ionsynergisticallycatalysed thermal decomposition
of NH4N03 has come from visible absorption spectro~copy.8~
Ammine,
nitrato-, and chloro-complexes of Cur1 and Nin and chloro-complexes of
Corl were detected in fused NH4N03.
Ammonium paramolybdate (APM) has been studied by d.tgs8 and by
analysis of the gaseous constituentssg of its thermal decomposition. Only
water molecules of hydration are eliminated during the first step and the final
stage is the oxidation of ammonia by MOO,, and not the elimination of
ammonia as had been previously suggested. Between 150 and 250C, NH,
and H,O are evolved in approximately a 2: 1 mole ratio. Using similar
technique^,^^,^^ the same author has shown that the first stage in the thermal
decomposition of (NH4),Cr0, is the production of (NH,),Cr,O,. The
dichromate proceeds to give CrO, and Cr,03 as the final involatile products;
NH,, H,O, N,, and N20 are evolved. It is well known that ammonium perchlorate (AP) is a widely used oxidizer in solid-fuel rockets. However, little
is known of the process by which granules of AP in the propellant grain
finally emerge from the rocket nozzle as combustion products. A time-offlight mass spectroscopic studyg2has attempted to identify the species in the
vapour phase above solid AP. Above a single-crystal surface of AP are equimolar quantities of NH3and HC104but the vapour above a powdered sample
83
84
86
86
87
8g
s1
92
H. Mauras, Compt. rend., 1973,276, C , 285.

M. G. Gibby, R. G . Griffin, A. Pines, and J. S. Waugh, Chem. Phys. Letters, 1972,
17,80.
L. Marosi and H. Theobald, Z . anorg. Chem., 1973,396, 185.
R. Kiimmel and F. Pieschel, 2.anorg. Chem., 1973, 396, 90.
A. G. Keenan and I. J. Ferrar, J. Phys. Chem., 1972, 76, 2844.
11-Hyun Park, Bull. Chem. SOC.Japan, 1972, 45,2739.
II-Hyun Park, Bull. Chem. SOC.Japan, 1972, 45, 2745.
11-Hyun Park, Bull. Ghem. SOC.Japan, 1972, 45, 2749.
Il-Hyun Park, Bull. Chem. SOC.Japan, 1972, 45,2753.
S. P. Tang and J. B. Fenn, J . Phys. Chern., 1973,77,940.
442

is a mixture of species of lower molecular weight. Presumably, dissociative
sublimation occurring in the subsurface interstices of the pressed material
precedes decomposition of the vapour.
The rate constant for the deprotonation of NH4Cl in anhydrous DMSO
(pH = 4-5) is the same order of magnitude (lo8 1mol-1 s-l) as that obtained in water and the reaction is promoted by a bimolecular reaction of
NH; with its conjugate base NH3.Q3
N2H4 and Derivatives. Interest in the use of hydrazine and its derivatives in
quantitative redox reactions continues. Conditions have been developed for a
direct potentiometric titration of Fe'' with hydrazine sulphate at room
temperature :94
NZH,
+ 4Fe3+
Nz
+=
+ 4H+ + 4Fe2+
Titrimetric procedures for the determination of K,Fe(CN), in alkalinemedia,

also using hydrazine sulphate, have been described.95 Determination of
hydrazine and its derivatives is also important. A back-titration technique
involving iodine monochloride in SM-HCl as the oxidant is simpler and of
wider applicability than previous methods.Q6
The effect of CoII, C d I , NiII, MnlIT, and FelI1 tetrasulphophthalocyanines on the autoxidation of N2H4 has been studied; only the CoII complex
showed a distinct catalytic effect.97 The complex [N,H,,cobalt tetrasulphophthalocyanine,O,] was postulated as an active intermediate in the reaction
and the kinetics followed the Michaelis-Menton law.
Careful attempts have been made to define the optimum conditions of formation of silver mirrors from silver nitrate and hydrazine sulphate, and the
heterogeneous kinetics examined?8 Q9
The reaction of diphenyl thiophosphinyl chloride with hydrazine hydrate in
ethanol yields diphenyl thiophosphinyl hydrazide:
PhaP(S)Cl
+ 2NaH4
--j
PhZP(S)NaHa
+ NZH4,HCI
On heating to 80 OC the product is converted into NN'-bis-(diphenylthiophosphiny1)hydrazine:

ZPhsP(S)-NH-NHa
PhaP(S)NHNHP(S)Ph, 3- NaHd
which may also be prepared from hydrazine hydrate and diphenylthiophosphinyl chloride under forcing conditions :loo
3NaH4 + 2PhaP(S)C1 + Ph,P(S)NH-NHP(S)Ph,
N,H,,HCI
93
O4
O5
O6
97
B. Bianchin and J.-J. Delpuech, Bull. SOC.chim. France, 1973, 34.

G. G. Rao, P. V. Rao, and G. B. B. Rao, Bull. Chem. SOC.Japan, 1972,45,3434.
P. V. K. Rao and G. B. B. Rao, Indian J. Chem., 1972, 10, 746.
P. N . K. Nambisan and C. G. R. Nair, Indian J. Chem., 1972, 10, 665.
D. M. Wagnerova, E. Schwertnerova, and J. Veprek-Siska, Coll. Czech. Chem. Comm,
1973, 38, 756.
J. Flechon and J.-P. Drexler, J. Chim. phys., 1973, 70, 769.

J. Flechon and J.-P. Drexler, Compt. rend., 1972, 275, C, 713.
loo H.-J. Jahns and L. Thielemann, Z . anorg. Chem., 1973,397,47.
O8
Elements of Group V
443
Little interest has been shown in the use of anhydrous hydrazine as a nonaqueous solvent. However, Table 2 lists the solubilities of the Group I and
Group I1 nitrates and perchlorates at 25 "C;lolthe solutions are claimed to be
stable and suitable for preparative work.
One report of the photoelectron spectrum of N,H, has interpreted the
measurements in terms of the molecule having a skew configuration (C,) and
Table 2 Solubilitieslg (100 g N2H4)-l of perchlorates and nitrates

in hydrazine at 25 "C
Cation
Li
Na
K
Rb
cs
Mg
Ca
Sr
Ba
NO3
61.2
117.8
28.0
35.8
23.1
39.8
40.0
61.2
88.5
C104
54.4
85.1
30.9
20.5
32.4
69.0
86.8
88.0
109.3
the valence orbitals being assigned as the ~LZ(T+),

3 b ( ~ - )4a(o),
,
4b(n-), and
5a(n+) orbitals in that order (n, 6,and T denote the nitrogen non-bonding
orbital, the N-N bonding orbital, and the NH, pseudo-rr orbital, respectively; and - combinations meansymmetricandantisymmetricwithrespect
to the C, axis).lo2Another report lo3gives the vertical ionization potentials
I(n -) = 10.70 eV and I(n +) = 10.02 eV and concludes that only bulky
substituents have any drastic effect on the dihedral angle. Both reports predict a dihedral angle of approximately 90, in agreement with experimental
data. CND0/2 calculations on 1,l-dimethylhydrazine and the 1$1-dimethylhydrazine-boron trifluoride complex reveal the existence of an equilibrium
between thegauche- (3) and trans- (4) forrns.lo4
A detailed study of the vibrational spectrum of tetramethylhydrazine in all

three phases has allowed the normal modes to be assigned.lo5By comparing
101 Zh. G. Sakk and V. Ya. Rosolovskii, Russ. J . Inorg. Chem., 1972, 17, 927.
lo2 K. Osafume, S. Katsumata, and K. Kimura, Chem. Phys. Letters, 1973, 19,
lo3 P. Rademacher, Angew. Chem. Znternat. Edn., 1973, 12,408.
M. Graffeuil, J.-F. Labarre, C. Leibovici, and E. Taillandier, J. MoZ. Structure,

1973, 15, 367.
J. R. Durig, R. W. MacNamee, L. B. Knight, and W. C. Harris, Znorg. Chem., 1973,
lo4
lo6
369.
12, 804.
444
the i.r. and Raman spectra of both the gaseous and solid states it was concluded that the molecule is in thegauche-form (C,)in all phases.
The phase diagram for N,H4 and its hydrates has been investigated.lo6
An extensive piece of worklo' has described the synthesis and properties of
methyldiazene (CH,N=NH) and the higher alkyl homologues. The compounds were prepared from the appropriate N-alkylhydroxylamine and
hydroxylamine-O-sulphonateion in aqueous alkaline solution. Basic physical
measurements were made (e.g.b.p., m.p., and AH,")and by comparison with
azomethane (CH3N=NCH3) it is suggested that liquid methyldiazene is
substantially hydrogen-bonded. A radical chain mechanism was proposed to
explain the kinetics of decomposition in the gas phase. Gas-phase i.r. spectra
of the parent and partially deuteriated molecules elucidated the distinctive
features of the gas-phase vibrational spectrum. U.v.-visible absorption data
helped to characterize the decomposition in acidic and basic media. A more
detailed studylo*of the i.r. spectra of CH3NNH, CH3NND, CD,NNH, and
CD3NND in the gas phase, at 77 K, and in nitrogen matrices has led to
the assignment of all fifteen fundamentals of each molecule.
No cis-di-imide was detected when the discharge products of N2H4were
examined in the solid and matrix-isolated states by i.r. and Raman spectroscopy. By consideration of HNNH, HNND, and DNND the five in-plane
vibrations of isolated trans-HNNH were determined and a tentative assignment was made for the out-of-plane torsion mode.loQAb initio MO calculations have been used to investigate the photochemical trans-cis isomerization of di-imide.l1 An in-plane motion of the hydrogen atoms was preferred for the ground and ,(n, n*) states whereas for the (n, w * ) states a
twisting about the N-N bond was involved in the most favourable pathway.
The results were seen as models for substituted derivatives.
Further characterization of the alkaline-earth pernitrides M3N4(M = Ca,
Sr, or Ba) and some related metal-nitrogen complexes has been carried out
using magnetic and CO uptake measurements.111 Hydrido-nitrides of Ca and
Ba have been prepared112 by the hydrogenation of the metal nitride and they
have been compared with the previously known Sr,NH. All three compounds
are ionic and Ca,NH and Sr,NH are isotypic but Ba,NH, although belonging
to the same cubic space group, has a smaller unit-cell dimension. A similar
hygroscopic compound of lithium, Li,NH, has been synthesized and found
to have the antifluorite structure.l13
Bonds to Carbon.-An
ingenious attempt to prepare five-co-ordinatenitrogen
G. Pannetier and F. Margineanu, Bull. SOC.chim. France, 1972, 3725.

M. N. Ackermann, M. R. Hallmark, S. K. Hammond, and A. N. Roe, Inorg. Chem.,
1972,11, 3076.
108 M. N. Ackermann, J. J. Burdge, and N. C. Craig, J. Chern. Phys., 1973,58,203.
loQ V. E. Bondybey and J. W. Nibler, J . Chem. Phys., 1973,58, 2125.
l10 N. C. Baird and J. R. Swenson, Canad. J. Chem., 1973, 51, 3097.
111 K.-H. Linke, R. Taubert, and T. Kruck, 2.anorg. Chem., 1973, 396, 1.
lla J.-F. Brice, J.-P. Motte, and J. Aubry, Compt. rend., 1973, 276, C, 1093.
113 J.-F. Brice, J.-P. Motte, and J. Aubry, Compt. rend., 1973, 276, C, 1015.
lo6
lo'
Elements of Group V
44 5
compounds by the reaction of bi-(2,2-biphenylylene)ammonium iodide ( 5 )

with lithium alkyls or oxygen bases was unsuccessful; instead, dehydroaromatics were formed.l*
Vibrational assignment of the rotational isomers (rotamers) of methyl
nitrite has been accomplished by means of a photochemical effect; vibrational
and electronic spectra were measured for the vapour phase and matrixisolated samples of H,CONO and D3CON0.11S
Heicklen has studied the photolysis of methyl nitrite,l16 which gives
methoxyl radicals :
CH30N0
+ hv
= C&O* 3. NO
In the lower atmosphere CH,O is an intermediate in the photochemical oxidation of hydrocarbons and may be important in the conversion of NO into
NO2. Thus, in an extension117 of the work of Wiebe et al., CH,ONO was
photolysed in the presence of NO, NO plus NO2, and NO plus 02.Nitromethane has also been photolysed in the gas phasel1* at 313 nm, the major
products being CH,ONO ($ = 0.22), HCHO (+ = 0.20), CH,NO (+ = 0.06),
and NO (+ = 0.10). When nitromethane decomposes thermally the same
basic reaction occurs :
CHaNO2 = CH3
+ NO2
The kinetics of the process in Ar have been followed11g and a rate constant
has been obtained for the first subsequent reaction:
CH,
+ NO2 = CHBO + NO
Similar results have been obtained for nitroethane,120and in addition it was

concluded that the ethyl radical decomposes to ethylene:
l14
115
116
117
D. Hellwinkel and H. Siefert, Annulen, 1972, 762, 29.

J. F.Ogilvie, J.C.S. Chem. Comm., 1973, 450.
H. A. Wiebe and J. Heicklen, J. Amer. Chem. SOC.,1973, 95, 1.
H.A. Wiebe, A. Villa, T. M. Hellman, and J. Heicklen, J. Amer. Chem. SOC.,1973,
11*
ll9
la0
K.Honda, H.Mikuni, and M. Takahasi, Bull. Chem. SOC.Japan, 1972, 45,3534.
95, 7.
K. Glanzer and J. Troe, Helv. Chim. Acta, 1972, 55, 2884.

K . Glanzer and J. Troe, Helv. Chim. Acta, 1973, 56, 577.

446
By the use of pulse radiolysis, the dissociation constant for the equilibrium:
C(N02)3H$ C(N02)i
+ H+ solvent
and the related kinetics have been obtained in various polar solvents.121
Analysis122 of the microwave spectrum of nitrosyl cyanide has given the
structure shown in Figure 1 ;the rotational constants are presented in Table
b
Figure 1 Bond parameters (distances/& in nitrosyl cyanide

(Reproduced from J.C.S. Chem. Comrn., 1973,241)
3. Detection of emission signals from interstellar formamide has created

renewed interest in the laboratory microwave spectrum of this molecule.
Measurements have been extended123to account accurately for centrifugal
distortion and a total of 22 new transitions involving J < 29 have been
measured for 14NH212CHU0for the ground vibrational state.
Table 3 Rotational constantslMHz for nitrosyl cyanide

Molecule
co
NOCN
16NOCN
NOPN
5384.39
5360.11
5205.87
5359.42
~
~
5040.63
5005.99
4882.49
5018.62
Tris(chloromethy1)amine and bis(chloromethy1)methylamine have been

preparedlZ4 by the action of PCl, on hexamethylenetetramine and
121
122
S. A. Chaudhri and K.-D. Asmus, J.C.S. Faraday I , 1972,68, 1010.

R. Dickinson, G. W. Kirby, J. G. Sweeny, and J. K. Tyler, J.C.S. Chem. Comm.,
1973, 241.
H. Kirchhoff and D. R. Johnson, J. Mol. Spectroscopy, 1973, 45, 159.

E. Fluck and P. Meiser, Chem. Ber., 1973, 106,69.
lg3W.
134
Elements of Group V
447
1,3,5-trimethylhexahydro-s-triazine,respectively :
M~N+\NM~
H2C,
,CH2
N
Me
2PC15 = MeN(CH2C1)2
C4P-N-CH'
Me
N-PC14
2-
Me
Several reactions of the products were investigated.

Two theoretical studies of the five isomers of diazomethane (CH2N2)have
been reported. Use was made of localized exclusive orbitals to understand
the bonding and of electrostatic potential maps in assessing positions of high
nucleophilicity in the isomers.12s Total dipole moments and 14Nquadrupole
coupling constants were calculated for each molecule.12s The electronic
structures of a series of unstable intermediates observed in flash photolysis
have been calculated by ab initio LCAO MO SCF methods.12' The equilibrium bond lengths for the linear species NNC, NCN, NCC, and CNC were
in good agreement with experimental results.
Bonds to Nitrogen.-The chemistry of co-ordinated azides has been reviewed.128
X-Ray analysis has shown the compounds KN,, RbN,, CsN,, and TIN, to
be isostru~tura1.l~~
They all crystallize in a tetragonal form of the CsCl type
(space group Z4lrncrn) with unit-cell dimensions as indicated in Table 4.
Table 4 Unit-cell parameterslA for metal azides (e.s.d.'s. in parentheses)
Compound
KN3
RbN,
CsN,
TIN
6.1 129(4)
6.3098(3)
6.5412(4)
6.208(1)
7.0943(6)
7.5188(4)
8.0908(5)
7.355(2)
Figure 2 shows a representation of the unit cell of KN,. Each metal atom has
eight nitrogen atoms as nearest neighbours in a distorted quadratic, antiprismatic arrangement at distances corresponding to the sum of the ionic
radii. The azide ions are all strictly linear and symmetrical, with N-N
distances of 1.17 A, within experimental error.
T. Hart, Austral. J. Chem., 1973, 26, 461.
T. Hart, Austral. J . Chem., 1973, 26, 477.
la' C. Thomson, J . Chem. Phys., 1973, 58, 841.
la8Z. Dori and R. F. Ziolo, Chem. Rev., 1973,73,247.
lag U . Miiller, 2.anorg. Chem., 1972, 392, 159.
125 B.
l Z 6B.
448
Inorganic Chemistry of the Mcrin-group Elements
Figure 2 Structure of KN,

(Reproduced by permission from Z . anorg. Chem., 1972,392,159)
Figure 3 Stereochemistry of the mercury atom in Hg(N,),

(Reproduced by permission from 2. anorg. Chem., 1973 399, 183)
Elements of Group V
449
The crystal structure of a-Hg(N,), has been solved13ousing data collected
at 140 K. Figure 3 shows the environment of the mercury atom, which is best
described as a seven-co-ordinate, distorted capped trigonal prism. Within
each N,-Hg-N,
unit the azido-groups make an angle of 143' to the
almost linear N-Hg-N
axis.
An electron-diffractionstudy131of methyl azide, CH,N,, has provided the
bond parameters listed in Table 5. Perhaps the most important point to note
Table 5 Bond parameters for methyl
azide
t(G-N)
r(N=N)
r(N=N terminal)
LCNN
1.468(5)
1.216(4)
1.130(5)
A
A
A
116.7(2)"
is that, like SiH,N,, methyl wide is bent, L C N N being ca. 117'.

The Raman spectra of single-crystal NaN, and polycrystalline LiN, have
been recorded either side of the temperature at which the rhombohedra1 to
monoclinic phase change occurs?32The results for NaN, are consistent with
previous work and for LiN, the phase transition is probably analogous to
that in NaN,. Similar studies on TIN, have indicated that an orthorhombic
distortion of the room-temperature tetragonal phase occurs at low temperatures.l= Thin films of lead azide show changes in the near-i.r. spectrum when
doped with TIN,, the changes being attributed to changes in the electronic
properties associated with azide vacancies which compensate for, and pair
with, substitutional T1 a ~ c e p t 0 r s . A
l ~new
~ theoretical treatment has allowed
analysis of the nuclear quadrupole hyperfine structure of the rotational
spectrum of cyanogen azide, NCN3.136
Pressure-change measurements of the thermal decomposition of LiN, show
induction, acceleratory, and decay ~ e r i 0 d s . The
l ~ ~ roles of Li atoms and of
the metal have been determined and the decomposition has been rationalized.
It was also found that pre-irradiation with U.V. light accelerated the thermal
decomposition. D.t.a. and t.g.a. of NaN, show that the first major stage of
decomposition is the evolution of nitrogen13' and a second, uncharacterized,
peak is also detectable. Photolysis of LiN,, to give molecular nitrogen, has
been studied1,* and a mechanism proposed involving a bimolecular reaction
between two excited azide ions.
130
lgl
U.Miiller, Z . anorg. Chem., 1973, 399, 183.
D. W. W.Anderson, D. W. H. Rankin, and A. Robertson, J. Mol. Structure, 1972,

14, 385.
131 Z.Iqbal, J. Chem. Phys., 1973, 59, 1769.
133 Z. Iqbal and M. L. Malhotra, J. Chem. Phys., 1972, 57, 2637.
134 S. P. Varma and F. Williams, J . Chern. Phys., 1973, 59, 912.
lg6G . L. Blackman, K. Bolton, R. D. Brown, F. R. Burden, and A. Mishra, J. Mol.
Spectroscopy, 1973,47,457.
138 E. G . Prout and V. C. Liddiard, J. Inorg. Nuclear Chem., 1973, 35, 2183.
13' H. Potvin and M. H. Back, Canad. J. Chem., 1973, 51, 183.
E. G. Prout and W. G . Sears, Inorg. Nuclear Chem. Letters, 1973, 9 , 31.
450
Inorganic Chemistry of the Maimgroup Elements
When equimolar amounts of a nitronium salt (NOtBFz) and an alkalimetal azide are mixed in an organic solvent (CCI, or CH,CN) the resulting
solution shows spectroscopic and chemical properties which are commensurate with the existence of nitryl azide, N402.139
The pure compound was
not isolated but the substance was suggested to be covalentlybound.Although
more stable than nitrosyl azide, it decomposes above -10 *C to give nitrous
oxide.
The N3radical is formed on irradiation of N2by 600 keV electron pulses;
the kinetics have been followed and a mechanism has been proposed.140In
order to differentiate between N! and Ni-, both of which have unpaired
electrons, unpaired spin densities have been calculated by the INDO method,
including a consideration of the anisotropic hyperfine intera~ti0n.l~~
On addition of amino-nitrenes to azo-compounds, amino-azimines are
produced. An X-ray analysis of a representative member of this class of compounds has provided conclusive proof of the geometry of the basic structural
unit.142The molecular structure is shown in Figure 4 for 2-(diphenylaminoaminy1io)-3,Ddioxo-4-phenyl-l,2,4-triazolidin-l
-ide. Two isolated conjugated
systems are separated by the single bonds C(7)-N(2) [1.497(7)A] and
C(8)-N(1) [1.445(8)A], and the three N-N distances are all significantly
shorter than the usual N-N distance (1.44A).
With the increased availability of pulse Fourier-transform spectroscopy,
15Nn.m.r. will become of increasing importance. 15N-15Ncoupling constants
have been obtained for a series of doubly labelled compounds and a correlation has been found with the hybridization of the nitrogen atom.'43
Bonds to Oxygen.-Aylett and co-workers have made an extensive
of
the reactions of seven silicon-halogen compounds with nitrogen oxides
chosen from N20, NO, N203, N204, and N205.Somewhat surprisingly,
no nitrato-species were formed in any reactions with N204and N205,SiF,
declining to react at all with either oxide. In general, the products were
siloxanes and their derivatives.
N,O. The absorption intensities of two i.r.-active lattice modes (at 67 and
117 cm-l) of crystalline N20have been measured.146Both the frequencies and
intensities are very close to those of solid C 0 2 ,any differences being explicable
in terms of differences in the quadrupole moments. Hisatsune has made a
detailed study14Bof the i.r. spectrum of N20 in alkali-metal halide matrices
(principally KCl, KBr, and KI) from 90 to 200K. N20 was conveniently
139
140
141
142
143
144
146
M. P. Doyle, J. J. Maciejko, and S . C. Busman, J. Amer. Chem. SOC.,1973, 95, 952.

J. W. Dreyer and D. Perner, Ber. Bunsengesellschaft phys. Chem., 1973, 77, 442.
G. F. Adams and F. J. Owens, J. Chem. Phys., 1973,58, 3532.
J. E. Weidenborner, E. Fahr, M. J. Richter, and K.-H. Koch, Angew. Chem. Internat.
Edn., 1973, 12,236.
S. Bulusu, J. Autera, and T. Axenrod, J.C.S. Chem. Comm., 1973, 602.
B. J. Aylett, I. A. Ellis, and J. R. Richmond, J.C.S.Dalton, 1973, 1523.
P. F. Krause and H. B. Friedrich, Chem. Phys. Letters, 1973, 18, 186.
I. C. Hisatsune, J, Chem. Phys., 1972, 57,2631.
Elements of Group V
451
generated in situ by the thermal decomposition of hydroxylamine hydrochloride or ammonium nitrate. The three fundamentals appeared as sharp bands
at room temperature, free of rotational structure, and the bands shifted to
higher frequency on cooling the host lattice. An analysis of the shape of vs
showed that there are two dominant trapping sites for N20 separated by an
Figure 4 Structure of the 2-(diphenylaminoamin~dio)-3,5-dioxo-4-phenyl-l,2,4triazolidin-1-ide molecule

(Reproduced by permission from Angew. Chem. Internat. Edn., 1973,12,326)
activation energy of 1.2 f 0.2 kcal mol-l and with a large entropy difference
of 9.0 f 1.0 e.u.
Simultaneous deposition of Li atoms and N,O in nitrogen matrices has
led to the identification of LiO and LizO by i.r. s p e c t r o ~ c o p yIsotopic
~~~
substitution showed Li,O to be linear. With the heavier congeners of lithium,
Na gave no oxide species and K, Rb, and Cs gave M,O only.148Unlike Li,O,
the other monoxides were bent, the angles in K,O and Rb20 being 160180' and in Cs20 130-140'. The oxidation of evaporated films of FeyNi, W,
and Pd involves rapid dissociative chemisorption, with evolution of N,,
at -78 0C.149
Lead did not take up N20 at all between -78 and +250 O C .
14'
R. C. Spiker jun., and L. Andrews, J . Chem. Phys., 1973,58,147.
148
R. C. Spiker jun., and L. Andrews, J. Chem. Phys., 1973, 58, 713.

S. A. Isa and J. M. Saleh, J. Phys. Chem., 1972, 76, 2530.
14s
so
452
The rate constant for the reaction:

H
+ N2O
= Nz
+ OH
has been determined.150On photolysing N 2 0 in cyclohexane the products are

N, and ROH in the ratio 1 :1 . ROH is mainly water with a little C-C6H110H.151
Kinetic measurements have been made of the decomposition of N,O with an
alternating current.152
Bond parameters have been derived for two electronic states of N20+from
the photoelectron spectrum of N20.153The results agree well with those obtained from the emission spectrum of N20+and confirm the validity of the
method of calculating molecular geometries from ESCA data.
NO. Further, detailed kinetic e ~ p e r i m e n t s have
l ~ ~ been carried out on the
simultaneous exchange reactions 15NO-N0z(nitrogen) and NO-H,1*0(oxygen). It was established from the different temperature coefficients and activation energies that separate N- and O-exchange mechanisms are operative
in this system. The rate law for N-exchange, R = k[NO][HNO,], implies a
transition state or an intermediate species HN,03 whereas the, somewhat
more speculative, rate law R = k[NO][H+] [HN02] and other evidence
suggest the possible formation of N20$ as an intermediate species in 0exchange. Similar investigations have been made155 for the system NOaqueous nitric acid. The simultaneous processes NO H,O .-+0 exchange
and NO + NOT + N exchange were explored using 15N0 and H2180. An
induction period occurred which was related to the production of HNO, in
the reversible reaction :
2N0
+ H+ + NO, + H2O + 3HN02
Nitrogen exchange was shown to be limited by NO-HNO, exchange, at an

overall rate that appeared to correspond to the reversible NO-HNO, reaction under equilibrium conditions. This same process will produce oxygen
exchange but NO-H,O oxygen exchange was found to occur at a much
greater rate, in a process that was assumed to proceed via HNOz without
involvement of nitrate, probably by a mechanism similar to that pertaining
to the all-nitrite system mentioned above.
A warning has been published of the dangerous nature of NO when it is
taking part in reactions with transition-metal atoms.156 Violent explosions
160
161
162
153
154
155
166
R. R. Baldwin, A. Gethin, and R. W. Walker, J.C.S. Faraday I, 1973, 69, 352.

Y . Hatano, K. Takeuchi, and S. Takao, J. Phys. Chem., 1973, 77, 586.
G. Lacoste, R. Bes, A. Savall, and P. Symonds, Compt. rend., 1973, 276, C, 189.
J. M. Hollas and T. A. Sutherley, Chem. Phys. Letters, 1973, 21, 167.
F. T. Bonner and S. Jordon, Znorg. Chem., 1973, 12, 1363.
S. Jordan and F. T. Bonner, Inorg. Chem., 1973, 12, 1369.
R. Middleton, J. R. Hull, S. R. Simpson, C. H. Tomlinson, and P. L. Timms, J.C.S.
Dalton, 1973, 120.
Elements of Group V
453
occurred with Mn vapour at approximately - 196 "C. However, co-condensation of beams of Li atoms157or the other alkali-metal atoms15*in high
dilution in argon at 15 K gave i.r. bands in the region of 1350 cm-I that were
attributed to the intra-ionic (N-0)mode and at 650-22Ocm-l which
were assigned to the inter-ionic M+-(NO)- vibration. Isotopic (15N)studies
suggested that Li+(ON)- has an acute triangular structure whereas the heavymetal species have a linear or bent arrangement in M+(NO)-. Photolysis of
Li+(ON)- produced Li+(ON)2-Li+, for which the i.r. spectrum was measured
and discussed. 1.r. spectroscopy has also assisted in the identification of isocyanate intermediates [Pt-NCO and (NCO)-] in the reaction of NO with
CO over a Pt/Al,O, cata1y~t.l~~
It has been found that ZnO, an n-type semiconductor, activated at 400C in high vacuum, is capable of reducing NO
at room temperature to N,0.l6O The reaction:
2N0
+ e-
= N20
+ 0-
leads to 0-ions which form electron traps on the surface. The interesting
speculation was made that further reaction of 0-with additional NO may
produce a complex whose structure may resemble a bidentate nitrate. The
rates of H atom reaction with NO have been determined by a modulation
technique.161 Ethyl radicals react with NO by successive addition to give
nitrosoethane and triethylhydroxylamine,162and trifluoromethyl radicals give
trifluoronitrosomethane and perfluorotrimethylhydr~xylamine.~~~
An elegant
direct proof has been obtained of predissociation of NO by using the recombination radiation as a highly specific light source which predissociates
Two MO calculations have been performed on the dimer (NO),.
VladimirofP5 has concluded that a cyclic structure is most stable. Shancke
carried out an ab initio calculation on the cis-isomer and exand
pressed reservation about some of the geometrical parameters calculated by
Vladimiroff and the strongly contracted basis set he used. In an additional
mechanism for the spin-forbidden a411-x211 transition of nitric oxide, consideration has been given to the coupling of two NO molecules and the
subsequent co-operative optical transition via a one-photon, spin-allowed,
electric-dipole mechanism.167It was concluded that this co-operative mechanism is as important as the conventional spin-orbit interaction mechanism.
D. E. Tevault and L. Andrews, J. Phys. Chem., 1973, 77, 1640.
D. E. Tevault and L. Andrews, J. Phys. Chem., 1973,77, 1646.
150 M. L. Unland, J. Phys. Chem., 1973, 77, 1952.
160 G. Kortiim and H. Knehr, Ber. Brcnsengesellschaft phys. Chem., 1973,77, 85.
161 R. Atkinson and R. J. Cvetanovic, Canad. J . Chem., 1973, 51, 370.
162 H.-S. Tan and F. W. Lampe, J. Phys. Chem., 1972, 76, 3303.
163 H.-S. Tan and F. W. Lampe, J. Phys. Chem., 1973,77, 1335.
164 hl. Mandelman, T. Carrington, and R. A. Young, J. Chem. Phys., 1973, 58, 84.
165 T. Vladimiroff, J. Amer. Chem. SOC.,1972, 94, 8250.
166 P. N. Shancke and J. E. Boggs, Chem. Phys. Letters, 1973, 21, 316.
167 G. L. Zarur and Y.-N. Chiu, J. Chem. Phys., 1972, 59, 82.
157
158
454

Configuration interaction studies of NO and NO+ have been carried out in
great detail.168 Full potential-energy curves were calculated in the BornOppenheimer approximation and the resulting energy difference and vibrational and rotational constants were compared with experimental results.
In this, and another paper:69 previously published photoelectron spectra of
NO are discussed. A
of the fundamental and first overtone bands of
NO has given the following expansion of the dipole-moment function in the
ground state of the molecule:
M ( x ) = -0.166
+ 2 . 5 4 ~- 1 . 9 9 (in
~ ~ Debye)
A fully resolved, Doppler-limited magnetic rotation spectrum of the R(13/2),,,

absorption line in the fundamental (Y = 0 --+v = 1) vibration-rotation band
of NO has been obtained171using a CW, tuneable PbSSe semiconducting
diode laser. Depolarization ratios and Raman scattering cross-sections are
reported for NO and NOF (and F,).172The molecular beam electric resonance
method was used to measure173 the hyperfine R-doubling spectrum of
l4Nl6Oand 15N160and the results were interpreted using degenerate perturbation theory. The X-band e.p.r. spectra of a gaseous mixture of 14N160,
14N170,and 14N1*0have been measured.174 The stabilization method of
Taylor has been used176to calculate the nature of the states of NO- corresponding to the lowest observed resonance. Spectroscopic constants for the
eight lowest electronic states of the NO+ ion have been tab~1ated.l'~
Nitrogen(rr1) Species Rubidium nitrite of purity 99.8 mass % has been made
by double decomposition of Rb,S04 and Ba(NO& with repeated recrystallization from water. Density, refractive index, and solubility in a range of
solvents have been measured.177The gas-phase reaction :
NO
+ NO2 + H,O
2HNO2
has been studied178in a stirred-flow Pyrex reactor in the temperature range

298.2-328.2 K. Saturated solutions of metal nitrites inDMF show evidence179
in the near U.V. for anion perturbation via ion association. E.s.r. studies reveal
nitroxide radicals to be produced under continuous illumination but flash
photolysis identified NO, as an earlier intermediate.
E. W. Thulstrup and Y.Ohm, J. Chem. Phys., 1972, 57, 3716.
J. L. Gardner and J. A. R. Samson, J. Electron Spectroscopy, 1973,2, 153.
170 G. Chandraiah and C. W. Cho, J. Mol. Spectroscopy, 1973, 47, 134.
171 F. A. Blum, K. W. Hill, and A. J. Strauss, J. Chem. Phys., 1973, 58, 4968.
172 J. M. Hoe11 jun., F. Allario, 0. Jarrett jun., and R. K. Seal jun., J. Chem. Phys.,
1973, 58,2896.
173 W. L. Meerts and A. Dymanus, J. Mol. Spectroscopy, 1972, 44, 320.
174 N. A. Ashford, F. H. Jarke, and I. J. Solomon, J. Chem. Phys., 1972,57, 3867.
175 H. Lefebvre-Brion, Chem. Phys. Letters, 1973, 19,456.
176 R. W. Field, J. Mol. Spectroscopy, 1973, 47, 194.
177 P. I. Protsenko and M. A. Savenkova, Russ. J. Inorg. Chem., 1973, 18,308.
178 R. F. Graham and B. J. Tyler, J.C.S. Faraduy I, 1972, 68, 683.
179 J. Cunningham and M. P. Ryan, Chem. Phys. Letters, 1972, 17, 179.
168
169
Elements of Group V
455
When NOCl reacts with the carbonates of Ag, Pb, and T1 the products are
C02, NO, and a mixture of the metal chloride and nitrate,lsOe.g.
2AgzCO3
+ 3NOC1 + 3AgCI + AgN03 + 2C0, + 2 N 0
AgNO, is produced by the reactions :
A 1 :1 crystallineadduct is formed between TiOCl, and NOCl which shows no

NO+ peak in the i.r. spectrum.lsl On heating to 50 "C TiOCl,,NOCl decomposes and TiC1,,2NOCl condenses out from the vapour phase. Only solid
solutions are formed between NOCl and HSiCI,, CH3SiCI,, and Si2C16.182
The kinetics of the reaction:
0
+ NOCl -+ C10 + NO
have been followedls3by e.s.r. but C10 was never detected.

NO,-N,O,. Another measurement has been madels4of the adiabatic electron
affinity of NO,: 2.50 f 0.05 eV; use was made of a crossed-beam method to
study the reaction :
Cs
+ NOa + Cs+ + NO,
A fascinating mass spectroscopic studylB6has been made of the N0,-N,04

system and the salient features are listed in Table 6 . It can be seen that the
system shows extensive polymerization beyond that of the dimer, and no
polar dimeric species was observed. Large gas imperfections have previously
been noted in low-pressure average molecular weight studies, and since species
of higher molecular weight than the dimer are presumably present in the
Table 6 Some of the peaks observed in the mass

spectrum of NO2
Mass (mle)
46
92
138
184
230
Ion
NO:
(NO,);
(NO,):
(No,):
(NO,),+
Intensity
-1
03
1 .O
4.8
0.03
0.90
Polarity
Polar
Non-polar
Non-polar
J.-P. Dumoulard and R. Perrot, Cumpt. rend., 1973,276, C , 1417.

B. Viard, J. Amaudrut, and C. Devin, Compt. rend., 1973,276, C , 1279.
lea C. Dubois and C. Devin, Compt. rend., 1973, 276, C , 1017.
lS3J. N. Dradley, D. A. Whytock, and T. A. Zaleski, J.C.S. Furaduy I , 1973, 69, 1251.
C. B. Leffert, W. M. Jackson, and E. W. Rothe,J. Chem. Phys., 1973,58,5801.
le6 S. E. Novick, B. J. Howard, and W. Klemperer, J. Chern. Phys., 1972,57, 5619.
lE0
456

equilibrium vapour then they will contribute to the 'gas imperfection'. Matrixisolation i.r. studies have suggested the existence of 'iso-N204' (6), a polar
molecule. In the present workls5 it was suggested that the i.r. absorption
attributed to (6) was due to trimer N,06 (7). The vibrational structure of the
2B,t 2A1 system of NO2 has been assignedls6to a progression in vb.

From new conductivity data for N204(Table 7) between -10 and +25 "C
Table 7 Conductivity of dinitrogen tetroxide
Conductivity/
T/"C
-10
-5
0
5
10
15
20
25
s1-1 cm-1
3.40 x 10-13
1.02 x
2.73 x
6.15 x
1.54 x
4.21 x
6.51 x
1.59 x
10-12
10-l2
10-l2
10-l1
10-l1
10-lo
and a redetermination of the dielectic constant between +5 and +25OC

(Table 8), it has been calculated that the enthalpy of ionization of N204:
NZO,
+ NO-+ + NO,
is 49.772 kcal mol-l, viz. a very endothermic process.187

When metals or metal compounds react with N20, in the synthesis of
anhydrous metal nitrates the first products which usually separate out,
frequently in crystalline form, are metal nitrate-N204 adducts. Much speculation has centred around the role of the N204in the crystal lattice, A preliminary report has now appearedlss of the crystal structure of thecopper
Table 8 Values of the dielectric constant for dinitrogen tetroxide
T/"C
Dielectric constant
2.003
10
2.053
15
2.240
20
2.498
25
2.787
J. L. Hardwick and J. C. D. Brand, Chem. Phys. Letters, 1973, 21, 458.

R . Audinos, J. Chim. phys., 1972, 69, 1263.
18* L. J. Blackwell, T. J. King, and A. Morris, J.C.S. Chem. Camm., 1973, 644.
186
lS7
Elements of Group V
457
nitrate-dinitrogen tetroxide adduct C U ( N O ~ ) ~ , NNo

~ O molecular
~.
N204is
present in the lattice. Rather, the copper atoms are co-ordinated by bridging
nitrate ligands to form anionic polymeric sheets and NOf ions occupy
available sites in the lattice. One other report has been made of a successful
X-ray analysis of an N,O, adduct : Fe(NO,),,l .5N20,.1sg Each asymmetric
unit has the composition 2Fe(N03),,3N,04 and the iron atoms are both
present in the well-characterized Fe(NO&. The compound may be formulated as 3NO+N0~[Fe(N03)~]2
but evidence was presented to suggest that the
cation is best represented as N40$+,Figure 5. In particular the i.r. spectrum
+ 0.09
,,5~q-
2.42=.:\
0.55
+0.21
Figure 5 Structure of the N40if group. (Interatomic distanceslA. Distances,

or -)
in A, above or below the NO, plane signified by
(Reproduced from J.C.S. Chem. Cumrn., 1973, 347)
shows none of the characteristic vibrations of NO3 and the NO+ vibration is
shifted from 2298 cm-l, for 'free' NO+, to 2235 cm-l in this compound. It
was also suggested that the N40i+cation may exist in nitric acid solutions of
N20,. The present preliminary reports suggest that this is a fertile field of
research.
Nitric Acid. The freezing-point depression by nitric acid of a eutectic perchloric acid-water system is only one-half of the depression caused by other
acids of equal molalities (HCI, HClO,, H2S0,). Since no solid solution of
HNO, is formed, it was concluded that nitric acid exists in dimeric form in
eutectic perchloric acid. Raman and U.V. spectra provide corroborative
evidence.lgOThe first cryoscopic study of DNO, has been reportedlgland allows
comparison to be made with HNO,. For example, the m.p. of DNO, is
C. C. Addison, L. J. Blackwell, B. Harrison, D. W. Jones, N. Logan, E. K. Nunn,
and S. C. Wallwork, J.C.S. Chem. Comm., 1973, 347.
l B oM. Ardon and L. Halicz, Inorg. Chem., 1973, 12, 1903.
lB1 A. W. Kureishi and P. A. H. Wyatt, J.C.S. Faraday I, 1972,68,676.
lED
458
-42.07 C, only 0.46 K lower than that of HNO,, and the molar enthalpy of
fusion (2370 f 10 kcaI mol-l) of DNO, is 5 % smaller than that of HNO,.
The reaction:
NZO5
+ HZO
2HNO3
has been shownlg2to proceed uia heterogeneous and gas-phase mechanisms,

and an upper limit for the rate constant (1.3 x
cm3molecule-l at 25 C)
has been estimated,
A compound has been isolated from the nitric acid-BF, system of composition HN0,,2BF3 and evidence presented to suggest that this adduct is
most accurately represented as NO$(BF&OH->g3 Kinetic and mechanistic
aspects of the oxidation of hydrobromic acid by nitric acid have been presented.lg4 Kinetic evidence suggests that the production of OH and NO3
radicals is concurrent in the radiolysis of aqueous 4.0 mol 1-1 nitric acid solu t i o n ~The
. ~ ~OH
~ and NO, radicals were presumed to result from the direct
interaction of ionizing radiation with water and nitric acid species (NOT and
HNOJ, respectively. The extraction of HNO, by the tetraethyldiamide of
heptyl phosphate (DAHP) and benzene has been studied.lS6
New measurements of the gas-phase U.V. absorption spectrum of nitric
acid vapourlg7have been used in conjunction with semi-empirical LCAOSCF calculations (including CI) to help define the lower electronic states of
HNOs>98CH,N02 and C,H6N02 were also studied and the results are presented in Table 9. It was concluded that the electronic transitions on these
Table 9 Electronic spectroscopic data for HN03, MeNO,, and EtNO,
Molecule
HNO,
MeNO,
EtN0,
Oscillator strength
Energy above ground state
Calculated
Calculated Observed
Observed
0.0
4.77
4.18
1.54 x
4.45
3.61 x 10-4
0.0
5.77
6.70
6.24
1.5 x 10-1 4.4 x 10-1
4.68
4.11
2 x 10-4
0.0
4.41
0.0
6.32
5.1 x 10-1
4.68
4.11
3.0 x
0.0
4.40
0.0
6.52
6.53
2.3 x 10-l 6.1 x 10-l
Transition
lA(no --t 7r*)
2A(O
--f
?T*)
2A(7ro-+
m*)
lA(no-+ n*)
2A(O3 w * )
2A(.t0 n*)
lA(no--t T*)
--+
2(o --+ 7r*)

2A(7ro --t 7r*)
molecules involve MOs which are predominantly localized on the terminal

NO, portions of the molecule, with the no and 7ro orbitals further localized on
the oxygens of the NO, group.
E. D. Morris jun., and H. Niki, J . Phys. Chem., 1973, 77, 1929.
R. Fourcade and G. Mascherpa, Bull. SOC.chim. France, 1972,4493.
lQ4 H. Feilchenfeld, S. Manor, and J. A. Epstein, J.C.S.Dalton, 1972, 2675.
lP6 R. W. Matthews, H. A. Mahlman, and T. J. Sworski, J. Phys. Chem., 1972,76,2680.
lQ6 V . I. Fadeeva, A. S. Litvincheva, and I. P. Alimarin, Russ. J . Inorg. Chem., 1973, 18,
Is*
lP3
331.
lS8
H. Johnston and R. Graham, J. P h p . Chem., 1973,77,62.

L.E.Harris, NuturePhys. Sci., 1973, 243, 103.
Elements of Group V
459
Nitrates. The most frequently reported physical property of metal nitrates is
the i.r. absorption spectrum. A good correlation has been found between the
vibrational frequencies of the NO5 ion in matrix-isolatedmonomers of several
nitrates MNO, and the polarizing power of the cation M+. It was important
to define the polarizing power as P = (z/r)/Serf,where S,,, = ( ~ z ~ ~ ~ ) / ( Y ~ / ~ J ) ,
z is the ionic charge, r is the ionic crystal radius in A, and I is the ionization
potential in eV. For molten nitrates the correlation breaks down but v1 could
be correlated with the product of thepolarizingpowerand thepolari~ability.~~~
The laser Raman spectra of AgNO, and TINO, have been investigatedzo0
from room temperature to a temperature 25C above the melting points.
Asymmetryof the v1 band was explained on the basis of coupling of vibrational
modes of adjacent NO3 ions. Spectral changes accompanying phase changes
were also discussed. Molten mixtures of AgNO, and TINO, have vibrational
frequencies nearly the same as those of the pure melts except for small changes
in the 700-750cm-1 region which are ascribed to the inhibition of backdonation of electrons to NOF from the cations in the mixed melt.201Vibrational spectroscopicresults reveal NaN03 ion pairs and solvated nitrate
ions to be present in solutions of NaNO, in D,0.202Assignments were made
and the association constant was measured; other physical measurements
were interpreted in terms of the derived model.
The kinetics and mechanism of oxalate ion decarboxylation in nitrate
melts have been investigated:203
C,Oi-
+ NO;
-+ NO,
+ COX- + CO,(gas)
The dependence of the reaction rate on the flow rate of the purge gas (Ar)
and of the initial C O f concentration was established. The NO: ion was
shown to be the oxidizing species in the decarboxylation process.
The growth rates of the CI and B phases in KNO, have been measured as a
function of the number of transformations and the temperature during the
cc --+ B and B -+ 0: tran~itions.2~~
It was found that the transformation rate
is influenced by recrystallization and relaxation processes. Dielectric transitions in MNO, (M = Li, Na, K, Rb, Cs, Ag, T1, or NH,) have characteristic temperatures which depend on the degree of packing of ions in the
crystal l a t t i ~ e . 2The
~ ~ same factor also influences the melting points of the
compounds.
Tetrabutylammonium nitrate coextracts approximately 1.4 moles of water
from a series of organic solvents;z06the corresponding perchlorate and tetraphenylboride extract 0 . 3 4 . 4 moles and zero moles of water, respectively.
lg9
M. H. Brooker and M. E. Bredig, J. Chem. Phys., 1973, 58,5319.
K. Balasubrahmanyam and G . J. Janz, J . Chem. Phys., 1972,57,4084.

K. Balasubrahmanyam and G. J. Janz, J. Chem. Phys., 1972,57,4089.
aoa J. D. Riddel, D. J. Lockwood, and D. E. Irish, Canad. J . Chern., 1972,50,2951.
203 R. Vilcu and N. Georgescu, Rev. Roumaine Chim., 1972, 17,1669.
204 Yu. G. Asadov and V. I. Nasirov, Sooiet Phys. Cryst., 1973, 17, 871.
,06 J. H. Fermor and A. Kjekshus, Acta Chem. Scand., 1973,27,915.
ao6 T. Kenjo and R. M. Diamond, J. Phys. Chem., 1972,76,2454.
2oo
201
460
In dilute THF-H,O solutions, vapour-pressure measurements show that

NaNO,, NaCIO,, and AgNO, are preferentially solvated by water, and
NaC10, and NaBPh, are preferentially solvated by THF.207A study has been
made of the solubility of NaNO, and KNO, in acetone-water mixtures.208
Hendrickson et al. have identified four non-potassium peaks (26.27,
14.59, 11.56, and 7.46 eV) in the X-ray photoelectron spectrum of KN0,.209
These peaks were assigned on the basis of the approximate MO calculations.
Dolin and Dyatkina210have also carried out MO calculations, using the
TDOA method, for NO; and their results compare well with those of an
unpublished ESCA study by V. I. Nefedov. The electronic absorption spectra
of NO; and transition-metal nitrato-complexes have been studied in detail and
the assignments supported by semi-empirical MO calculations.211Two of the
important conclusions were :
(a) The 300 nm absorption band of NO; contains triplet t singlet character
of nature
c
and/or
c lrl,
and (b) The low-energy spectra of transition-metal nitrato-complexes are
dominated by charge-transfer transitions. Absorption spectra of pentaerythritol tetranitrate, C(CH,0N0,)4, in acetonitrile showed bands at 193-5,
260.0, and 290.0 nm.212 MO calculations aided the following assignment :
193.5 (T -+ T* localized in the -NO, groups), 260.0 and 290.0 nm ( n -+ T*
transitions of the -NO2 groups).
Strong support for an oxygen-atom mechanism in the radiation-induced
decomposition of KNO, to KNO, has been obtained from l*O and 15N
substitution studies. Quantitative measurements were made by laser Raman
Table 10 Multicomponent systems containing nitrate andlor nitrite
System
K+ ,Na+, NO;, NO;, H 2 0
NH4+,Na+, NO;, HzO
K+, Li+, C1-, NOS
Cs+, K+, Ba2+,NO,
Cs+, Ti+, Ba2+,NO;
Li+, Cs+,NO;, SO:Na+,NO;,NO;,H20
Rb+,Cs+, NO;, NO;
Ca2+,NHZ, CIO;, NO;, H 2 0
Na+, NO;, BunOH, H 2 0
K+, Ag+, NO;, SO:NH;, Ca2+,NO;, H,O
Reference
215
216
217
218
218
219
220
221
222
223
224
225
C. Treiner, J.-F. Bocquet, and M. Chemla, J. Chim. phys., 1973, 70,472.

H. Hoppe and F. Winkler, 2. Chem., 1973, 13,304.
209 W. H. Morrisonjun., and D. N. Hendrickson, Znorg. Chem., 1972,11,2600.
%lo
S . P. Dolin and M. E. Dyatkina, J . Struct. Chem., 1973, 13, 906.
211 H. J. Maria, J. R. McDonald, and S. P. McGlynn, J. Amer. Chem. SOC.,1973, 95,
207
208
218
1050.
P. A. Mullen and M. K. Orloff, J . Phys. Chem., 1973, 77, 910.
Elements of Group V
461
spectroscopy.213 Sr(NO&, and Ba(NO3),, melt-recrystallized and partly
decomposed, gave e.s.r. spectra assigned to NO:- with hyperfine splitting
slightly different from that of NO!- in X-irradiated Sr(N03),. The NOgapparently resides in the decomposition product, SrCO,, from atmospheric
C02.It was proposed that NO:- is a decomposition intermediate in nitrate
melts.214
A large number of multicomponent systems involving nitrate ion have
been studied and are summarized in Table 10?15-225
Miscellaneous N-0 Species. The literature contains some discussion of the
structure and bonding in Angeli's salt. An X-ray analysis has now been
Figure 6 DistanceslA and angles/" in the N,O$- ion (E.s.d.'s are about
0.005 A and 0.3')
reported for sodium trioxodinitrate(I1) monohydrate, Na,N,0,,H,0.226 The

anion is crystallographically planar, and Figure 6 shows its geometry together with the bond parameters. The N-N distance, 1.264 A, is close to that
found in azobenzenes and corresponds to a double bond, as suggested by
Addison and co-workers some years ago, on the basis of U.V. spectroscopic
data.
G. E. Boyd and M. H. Brooker, J. Amer. Chem. SOC.,1973,95,4816.
L. G. Harrison and H. N. Ng, J.C.S. Faraday I , 1973,69,1432.
a15 A. M. Babenko, Russ. J. Znorg. Chem., 1972, 17, 1609.
216 A. G. Bergman and L. F. Shulyack, Russ. J. Znorg. Chem., 1972,17, 593.
217 I. I. Il'yasov and Yu. G. Litvinov, Russ. J. Znorg. Chem., 1972, 17, 607.
218 P. 1. Protsenko and G . F. Shmel'kova, R i m . J. Znorg. Chem., 1972, 17,452.
219 G. G. Diogenov and R. 0. Mavridis, Russ. J. Inorg. Chem., 1972, 17,449.
220 Ya. S. Shenkin, S. A. Rushnova, and N. A. Rodionova, Russ. J . Inorg. Chem., 1973,
18, 123.
221 P. I. Protsenko and L. S. Grin'ko, Russ. J . Inorg. Chem., 1973, 18, 120.
2 2 2 S . I. Vasil'eva and I. N. Lepeshkov, Russ. J . Inorg. Chem., 1973,18,429.
2 2 3 N. Yui, Y. Kurokawa, and M. Nakayama, Bull. Chem. SOC.Japan, 1973, 46, 1027.
2 2 4 M. L. Saboungi, C. Vallet, and Y . Doucet, J. Phys. Chem., 1973, 77, 1699.
2 2 5 R. Kummel and A. Schubert, 2. Chem., 1973, 13,232.
2 2 6 H. Hope and M. R. Sequeira, Inorg. Chem., 1973, 12,286.
213
214

462
CNDO/s-CI calculations have been carried out on a seresi of compounds
containing the -NO2 moiety (NO;, NO;, nitramide, ethyl nitrate, HNO,,
methyl nitrate, and nitromethane) and the lower electronic states have been
~pecified.2~
The nitrosyldisulphonate ion-radical (8) has been identified by
e.s.r. in X-irradiated single crystals of Fremys salt (potassium hydroxylaminedisulphonate).228The microwave spectrum of nitroxyl, HNO, has been
observed and a n a l y ~ e dthe
, ~ ~results
~
being presented in Table 11. The structures, standard heats of formation, and ionization energies of the six known
N-0-F
compounds (FNO, FN02,FON02,ONF,, ONNF,, and 0,NNF2)
have been calculated using the semi-empirical MO method230and are in excellent agreement with available experimental data. Since no data about the
Table 11 Data derivedfrom the microwave spectrum of nitroxyl

radical, HNO
Rotational constants
Dipole moments
Quadrupole coupling constants
A = 553 903.0 2.7 MHz

B = 42308.52 f 0.10MHz
C = 39 169.46 f 0.10MHz
PtQtal = 1.67 f 0.03D
= 1.03 f 0.01 D
p b = 1.31 f 0.02 D
Xaa = 0.36 f 0.56 MHz
Xbb = -5.46 f 0.30 MHz
~ c=
c 5.10 f 0.26 MHz
compounds were included as input, the authors were sufficiently confident

to embark on a study of eleven postulated N-0-F
compounds. Only four
were considered likely to be stable: FONO (which has since been claimed),
FO,NO, F2N(OF), and F,N(02F). All are suitable for attack by ingenious
synthetic chemists
Nitrogen Oxides and Atmospheric Chemistry. Over the past few years it has
become clear that nitrogen oxides play a significant role in the chemistry of
our atmosphere. It therefore seems pertinent to include a brief summary of
relevant research in this Report. Two features require careful examination:
the detection of the reactive species (often in very low concentrations) and the
measurement of the rates at which they react.
L. E. Harris, J . Chem. Phys., 1973, 58, 5615.
P. J. Harnrick, H. Shields, and T. Gangwer, J. Chern. Phys., 1972,57,5029.
2ap S. Saito and K. Takagi, J. Mol. Spectroscopy, 1973, 47, 99.
*30 P. S. Ganguli and H. A. McGee jun., Inorg. Chem.,1972, 11,3071.
227
228
Elements of Group V
463
The important u.v.-filtering action of ozone has caused concern about the
factors which control its concentration in the stratosphere. It has been suggested that NO and NO, may control the formation and destruction of
stratospheric 0,and a recent study has reported231the presence of NO in a
mean mixing ratio of 1 .O f 0.2 parts per thousand million from 11 to 26 km.
The NO is probably produced by the reaction:
NzO
+ O(l0) -+
2NO
and the rate constant for this reaction has been measured232together with
kinetic data on the reactions of 0,with NO and with NO,. Another possible
source of NO is the reaction:
NO^
-+ NO
o(3~)
+ 0,
which has been studied by flash photolysis-resonance fluorescence.233OH

and NO and/or NO, are important in several atmospheric processes, including the production of photochemical smog. In particular, the termolecular reactions :
OH
OH
+ NO + M
+ NOz + M
+M
HN03 + M
4 HNOZ
have been studied by the detection of OH radicals with e.s.r.,% and fluorescence235#236
techniques. Also important is the photolysis of NO,, which may
be represented by:
NOz
+ hv + NO + 0
but which it has been generally agreed proceeds via a nine-stage mechanism.
Elementary rate constants have been evaluated when NO, is photolysed in
1 atm of N,237
and the importance of photodissociation rates has been discussed in the system under high pressure (up to 1000 atm).238A good method
for generating the hyperoxyl radical, HO,, by the photolysis of N20-H20
mixtures has enabled the reaction:
HOS
S31
238
233
234
235
236
237
z38
+ NO
NOS
+ OH
R. A. Toth, C. B. Farmer, R. A. Schindler, 0. F. Raper, and P. W. Schaper, Nature

Phys. Sci., 1973,244, 7.
Y. H. Ghormley, R. L. Ellsworth, and C. J. Hochanadel, J. Phys. Chem., 1973,77,
1341.
D. D. Davis, J. T. Herron, and R. E. Huie, J. Chem. Phys., 1973, 58, 530.
A. A. Westernberg and N. de Haas, J. Chem. Phys., 1972, 57,5375.
F. Stuhl and H. Niki, J. Chem. Phys., 1972, 57, 3677.
J. G. Anderson and F. Kaufman, Chem. Phys. Letters, 1972, 16, 375.
A. B. Harker and H. S. Johnston, J. Phys. Chem., 1973, 77, 1153.
H. Gaedtke, H. Hippler, and J. Troe, Chem. Phys. Letters, 1972,16, 177.
464
to be studied in
The NO-NO, interconversion has also been examined in the presence of methylperoxyl radicals, which may be generated by
photolysis of exhaust fumes in urban areas.24o
Oxidation of atmospheric gases (e.g. SO,) to form aerosols has been thought
to occur with 0, as the oxidizing agent. Kinetic evidence, using the stoppedflow technique, has been obtained to support the theory that the oxidant is
0,.2Vibrationally
41
excited nitrogen plays a number of important roles in
determining the nature of the lower thermosphere. In the reaction:
N(4S)
+ NO
+ O(3P)
-+N2cv)
Raman spectroscopy has

that 25 f 3 % of the available energy
(3.27 eV) appears as vibrational energy. It was shown that the vibrationally
excited N2 is a primary product of the reaction and is not produced by collisions of translationally hot oxygen atoms with N,.
Bonds to Fluorine.-NF,-N,F,. Three ab initio SCF calculations have been
reported for the NF, radical. It has been
that, provided a goodquality basis set is used, the single-annihilation UHF method can provide
accurate values for most charge- and spin-dependent observable properties of
open-shell molecules such as NF,. Geometrical predictionszd4for this species
using different gaussian orbital basis sets have been compared and the values
( e g . bond angle ca. 102") are in reasonable agreement with the experimental
values (104.2'). Using a contracted gaussian basis set of double 5 plus polarization quality, a wide range of physical properties has been calculated245
together with orbital energies and population analysis for NF,.
to ignite the
Vibrational excitation from a pulsed CO, laser has been
explosion of mixtures of N2F4 and H2. It was concluded: (a) pulsed i.r. laser
radiolysis is a viable method for obtaining a fast non-equilibrium increase in
the energy of a system; (b) vibrational excitation results in chemical reaction
more rapidly than if the same amount of energy were added thermally.
The shock-initiated thermal dissociation of tetrafluorohydrazine:
in excess Ar and Nz has been investigated247over the temperature range

351-453 K at total pressures 1.0-9.4 atm in Ar and 0.69-12.0 atm in N,
239
a40
241
242
243
a44
a45
a46
a47
R. Simonaitis and J. Heicklen, J. P h p . Chem., 1973, 77, 1096.

C. W. Spicer, A. Villa, H. A. Wiebe, and J. Heicklen, J. Amer. Chem. SOC.,1973,95,
13.
S. A. Penkett, Nature Phys. Sci., 1972, 240, 105.
G. Black, R. L. Sharpless, and T. G. Slanger, J . Chem. Pliys., 1973, 58,4792.
R. D. Brown, F. R. Burden, B. T. Hart, and G. R. Williams, Theor. Chim. Actu,
1973, 28, 339.
C. Thomson and D. A. Brotchie, Chem. Plzys. Letters, 1972, 16, 573.
S. Rothenberg and H. F. Schacfer tert., J . Amer. Chem. SOC.,1973, 95, 2095.
J. L. Lyman and R. J. Jenson, J . Phys. Chem., 1973, 77, 883.
E. Tschuikow-Roux, K. 0. MacFadden, K. H . Jung, and D. A. Armstrong, J . Phys.
Chem., 1973,77,734.
Elements of Group V
465
and the results have been discussed in terms of the RRKM theory of unimolecular reactions. When the free radicals H and NF, react, electronically
excited NF is produced, probably via an elimination reaction.248
An important mass-spectroscopic investigation249of N2F4 differs significantly from previous studies. In particular, dissociation of N,F, into NF,
at 300 K at very low pressures, for which the degree of dissociation should
be almost 100% at equilibrium, was found to be a slow process. Useful
thermochemical data were derived: D(F,N-NF,) = 0.91 f 0.1 eV (21.6 f
3.2 kcal mol-l); D(FN-F) = 3.15 f 0.10 eV (72.8 f 2.3 kcal mol-l);
I.P.(N,F4) = 12.00 f 0.1 eV; I.P.(NF,) = 11.76 f 0.1 eV; and I.P.(NF) =
12.24 f 0.1 eV.
MisceZZaneous N-F Species. A kinetic study of the dissociation of NF, in
excess Ar, using a shock tube-spectrophotometric technique, has shown250
that the reaction may be represented by:
and the Arrhenius parameters were derived.

Improved
The syntheses of NF,Cl and N,F, have been described in
yields in the preparation of difluoraminocarbonyl chloride (9) have allowed
Synthesis was achieved
some of its chemistry to be pursued in more
by photolysis (4-6h) of N2F4 with oxalyl chloride. New difluoraminocarbonyl pseudohalides NF,C(O)CN, NF,C(O)NCS, NF,C(O)NCO,
NF,C(O)SCF,, and NF,C(O)ON(CFJ, have been prepared from NF,C(O)Cl
with AgCN, AgNCS, AgNCO, Hg(SCF3),, and Hg{ON(CF,),),, respectively. Nearly quantitative conversion into perffuorourea, (NF,),CO, occurs
with excess Ag,O at 0 "C or HgO at -78 'C. When the adduct HNF,,KF
reacts with sulphinyl fluoride, FS(0)NF2 is produced,253and the product has
sufficient stability to be isolated and characterized by spectroscopic techniques. However, attempts to prepare CF3S(0)NF, and C,F,S(O)NF, gave
N,F, and the esters CF,S02SCF3 and CF,SO,C,F,. HF and DF chemical
laser emission has been observed254owing to elimination from NN-difluoromethylamine, CH3NF2,and its deuteriated analogues.
248
249
250
251
25z
253
z54
J. M. Herbelin and N. Cohen, Chern. Phys. Letters, 1973, 20, 605.

S. N. Foner and R. L. Hudson, J . Chem. Phys., 1973,58, 581.
K. 0. MacFadden and F. Tschuikow-Roux, J. Phys. Chem., 1973,77,1475.
L. M. Zaborowski, R. A. DeMarco, and J. M. Shreeve, Inorg. Synth., 1973, 14, 34.
K. J. Wright and J. M. Shreeve, Inorg. Chem., 1973, 12, 77.
R. A. DeMarco and J. M. Shreeve, Inorg. Chem., 1973, 12, 1896.
T. D. Padrick and G. C. Pimentel, J. Phys. Chem., 1972, 76, 3125.
466
Configuration interaction studies of N F (isoelectronic with 0,) and NFt

have enabled full potential-energy curves, wavefunctions, and the resulting
physical constants to be calculated.256The photoelectron spectrum of NSF,
has been recorded and, by comparison with the bands of NSF together with
semi-empirical calculations, the first band has been assigned to ionization
processes involving the 7 e ( ~ )
A force-field
has been used to
help in assigning v5 in trifluoramine oxide, NOF,, to a band at 513 cm-l.
Bonds to Chlorine and Iodine.-The first band in the photoelectron spectrum

of NSCl has been assigned to an ionization process involving the 16a'(a)
Detonation velocities of N,Cl have been studied.25s
Conditions have been reported for the preparation of N-di-iodomethylamine and N-iododimethylamine. 1.r. spectral evidence suggests a polymeric
structure for the di-iodomethylamine adducts with nitrogen donors such as
CH,NH,,but iododimethylamineis thought to be monomeric.2591.r. measurements for 14N13,1,NH3; l5NI,,l5NHg; 14NI,,pyridine; and 14N13,1,ND3have
The absorption
been reported and approximate force constants
frequencies were assigned on the basis of a C,, skeleton of Z , X Y , . Similar
studies have been carried out on (CH3N12),12and (CH&,NI,I, and it was
concluded that the compounds were monomeric.261
2 Phosphorus
Element.-The bonding in P, and the unstable nitrogen analogue, N,, has been
studied by ab initio and semi-empirical SCF-MO calculations.262The
former show that P4 is stable with respect to 2P2 by 35 kcal mol-l while
N, is unstable by 126 kcal mol-l when compared with 2N2. INDO calculations on the other hand predict that in both cases the tetra-atomic species
would be the more stable. Photoelectron spectra of P4 can be interpreted on
either model and inclusion of 3d orbitals is not considered to add significantly
to the description of the bonding in P4.
Vapour-phase Raman spectra for P4at 570 K and As, at 950 K have been
analysed to give general quadratic force constants.26sThe values of &, fir,
and& are respectively 2.07, -0.13, and 0.12 mdyn A-1 for P4 and 1.50,
-0.08, and 0.1 1 for As,.
Syntheses involving elemental phosphorus have been reviewed, placing
emphasis on newer reactions,264and processes involving phosphorus that have
256
256
257
259
260
261
262
26a
264
A. Anderson and Y.Ohm, J. Mol. Spectroscopy, 1973, 45, 358.

D. 0. Cowan, R. Gleiter, 0. Glemser, and E. Heilbronner, Helv. Chim. Acta, 1972,
55,2418.
C. V. Berney and A. D. Cormier, J. Chem. Phys., 1973, 58,4709.
C. Paillard, G. Dupre, and J. Combourieu, J . Chim. phys., 1973, 70, 811.
J. Jander, K. Knuth, and W. Renz, 2.anorg. Chem., 1972, 392, 143.
K. Knuth, J. Jander, and U. Englehardt, 2.anorg. Chem., 1972, 392,279.
K. Knuth, W. Renz, and J. Jander, 2. anorg. Chem., 1973,400, 67.
M. F. Guest, I. H. Hillier, and V. R. Saunders, J.C.S. Faraday 11, 1972, 2070.
Y.M. Bosworth, R. J. H. Clark, and D. M. Rippon, J. Mol. Spectroscopy, 1973,46,
240.
H. Staendeke, Chcm.-Ztg., 1972, 96,494.
467
Elements of Group V
become industrially important during the past few years are discussed.26S
Oxidation of red phosphorus with hydrogen peroxide in aqueous ammonia
gives, in addition to other compounds, amidodiphosphate(1v) species26s
according to the equations:
0 0
2P
4NH3
+ 4HzO2
II II
(NH&[O-P-P-NH2]
I I II
3H20
0 0
31P n.m.r. and vibration data are given for the new compounds.
Phosphides.-Thermal decomposition of Nap, gives the new, orthorhombic,
Na,P,,. The orange compound267belongs to the space group Pnab and contains isolated P;: units in the lattice (see Figure 7); the unit is chiral and both
Figure 7 The structure of the Piigroup in Na,Pll

(Reproduced by permission from Naturwiss., 1973, 60, 104)
mirror images are present. Powder diffraction data show that CaP and SrP
together with CaAs, SrAs, and EuIIAs crystallize with the Na202structure
and contain Pi- or As:- units,268but the corresponding barium phases do not
exist. Crystal data indicate that in SrP, there is an infinite two-dimensional
array of condensed six-membered rings while in Ba3P,, (monoclinic, P2,/a)
isolated P:- units can be discerned.269
265
266
267
268
269
31
G. Heymer and H.-D. Wasel-Nielen, Chem.-Ztg., 1972, 96, 475.

H. Falius, 2.anorg. Chem., 1973, 396, 245.
W. Wichelhaus and H. G. von Schnering, Naturwiss., 1973, 60, 104.
A. Iandelli and E. Franceschi, J. Less-Common Metals, 1973, 30, 21 1.
W. Dahlmann and H. G. von Schnering, Naturwiss., 1973, 60,429.
468
Mass spectrometric studies270in the C-P system give the following data:
AH&(reaction)/kcal mol-l
+ C(s) CP
P + 2C(s) + C2P
Pa + C(s) -* CP,
P
P2
--f
+ 2C(S) + cap,
AHP(product)/kcal mo1-I
48.6 f 1.6
128.4 f 1.7
71.9 f 2.0
151.7 f 4.1
54.0 f 2.0
96.7 f 2.5
55.8 f 4.0
98.5 f 4.5
A pyrocarbon with phosphorus present in substitutional solid solution can be

prepared271by codeposition from a CH4-PCI3-H2 mixture at temperatures
between 1220 and 173OOC. Details for the preparation of the pyrite type of
Sip, have been given.,', The structure of the tin phosphide SnP,, space group
R h ,consists of layers of condensed puckered P6 rings stacked parallel to the
c - a ~ i s The
. ~ ~ tin
~ atoms between the layers have a distorted octahedral
environment (three Sn-P distances of 2.662 A and three of 2.925 A). Within
the P6 rings the P-P distances are 2.222 A, the PPP angles are 99.1'. Powder
data show that GeP, is isostructural.
A new vanadium phosphide V4P3has been identified during phase equilibrium studies in the V-P-C ternary system at 1000C.274In addition, three
previously unknown ternary phases V5+,P,Cl-,, v,6P3c,-,.,
and V4P& have
been described. The latter is an example of a new structural type based on
packing of trigonal prismatic and octahedral units. The structure of Nb,P,
(orthorhombic, Pbam assumed) can best be described as consisting of interconnected Nb,P triangular prisms with additional Nb atoms between the
prisms.275
Magnetic measurements over a temperature range are given for CrP,
which from powder data belongs to the space group Pnma.276Mixtures of
Ni,P and Ni6P, are obtained277when nickel sheets are phosphidized with
PCI, vapour in the temperature range 4O0-65O0C. Data on rare-earth
phosphides have been
including methods of preparation, thermal
stability, and deviation from stoicheiometry. In addition, their magnetic and
electrical behaviour together with some thermodynamic data are covered.
The readily hydrolysed calcium iodophosphide Ca,PI and its arsenic
analogue can be obtained from the elements at 700-750 0C.279
Compounds
271
272
273
274
275
276
277
278
279
J. Kordis and K. A. Gingerich, J. Chem. Phys., 1973, 58, 5058.

S. Marinkovic, C. Suznjevic, A. Tukovic, I. Dezarov, and D. Cerovic, Carbon, 1973,
11, 217.
P. C. Donohue, Znorg. Synth., 1973, 14, 173.
J. Gullman and 0. Olofsson, J. Solid State Chem., 1972, 5 , 441.
H. Boller, Monatsh., 1973, 104,48.
S. Anugul, C. Pontchour, and S. Rundqvist, Acta Chem. Scand., 1973, 27, 26.
K. Selte, A. Kjekshus, and A. F. Andersen, Acta Chem. Scand., 1972, 26,4188.
Y. Sasalti and S. Ueda, 2. anorg. Chem., 1973, 396, 319.
K. E. Mironov, I. G. Vasileva, and T. G. Pritchina, Rev. Chim. minirale, 1973, 10,
383.
C. Hamon, R. Marchand, and J. Lang, Compt. rend., 1972, 275, C, 1511.
469
with the stoicheiometry Ge,,A,X8, where A = P, As, or Sb and X = C1,
Br, or I, can be synthesized either from the elements or from germanium and
the Group V halide in a sealed quartz tube at high temperature.280X-Ray
data show structures similar to that of the gas hydrates, where the Group V
element and germanium build up a three-dimensional 46-atom framework of
tetrahedrally bound atoms with the eight halide ions situated in the cavities.
The compounds show semiconductor behaviour.
The mixed species Ti,PSb, Zr,PSb, and Hf,PSb have been prepared and
shown to crystallize with the Ti,SC structure;281TiP and TiAs on the other
hand form a continuous solid solution with partial ordering of the phosphorus
and arsenic atoms at 800 "C. Two new mercury halogeno-phosphides,
I-Ig,P,Cl and Hg,P,Br, result when the mercury dihalide is heated in a sealed
silica tube at 5OO0C with the stoicheiometric amounts of mercury and
phosphorus.282Both compounds are black semiconductors which are stable
in hydrochloric and nitric acids.
Elements of Group V
Hydrides.-Ab initio calculations for PH, using three different Gaussian

basis sets are compared with earlier calculations.283Population analyses
indicate little charge separation in the molecule and the addition of dcharacter
has little net effect on the P-H bond. Similar calculations284imply that the
calculated barrier to inversion in PH, is very sensitive to the inclusion of dorbitals. The latter calculations also showed that pyramidal geometry is
expected for PM, and PF, and their ground ionic states.
Details for synthesizing PH, from aluminium phosphide have been given,285
and the chemistry and physical properties of phosphine have been reviewed.286
Short sections on the higher phosphines are also included.
1.r. spectra of two crystalline forms of PH, and PD, have been reported.287
At 35K, broad, structureless absorption bands are observed but at 3 0 K
many sharp bands result, and it is suggested that the low-temperature modification may have as many as 12 molecules in the unit cell, occupying six
different sets of sites. Ab initio calculations288of the vibrational frequencies
and force constants for PH, gave the latter ca. 20% too high, but as a harmonic force field was assumed, agreement is perhaps reasonable.
31Pand lH n.m.r. spectra have been measured for PH,, P,H,, P,H,, and
mixtures of higher members of the series between -60 and -93 0C;289the
280
281
282
283
H. Menke and H. G. von Schnering, 2.anorg. Chem., 1973, 395, 223.

H. Boller, Monatsh., 1973, 104, 166.
P. C. Donohue, J . Solid State Chem., 1973, 6,587.
J.-B. Robert, H. Marsmann, L. J. Schaad, and J. R. Van Wazer, Phosphorus, 1972,2,
11.
284
L. J. Aarons, M. F. Guest, M. B. Hall, and I. H. Hillier, J.C.S. Furaday 11, 1973,69,
286
R. C. Marriott, J. D. Odom, and C. T. Sears, jun., Inorg. Synth., 1973, 14, 1.

E. Fluck, Forrschr. Chem. Forsch., 1973, 35, 1.
M. D. Francia and E. R. Nixon, J. Chem. Phys., 1973, 58, 1061.
W. Walker, J . Chem. Phys., 1973,59, 1537.
P. Junkes, M. Baudler, J. Dobbers, and D. Rackwitz, 2. Narurforsch., 1972, 27b,
643.
288
287
288
289
1451.
470
data for P2H4 have been analysed as an A2XX'Ai system. The chief reaction
product from KPH, and PF,Br is H,PPF, but a mass-spectrometric investigation has shown the presence of small amounts of the unknown H,PPHF.290
Secondary production of the compound in the spectrometer was eliminated
as a possible mode of formation. N.m.r. evidence291shows that 1,2-diphenyldiphosphine is present in equilibrium with its dismutation products, PhPH,
and (PhP),. Values of coupling constants and temperature-dependence
studies indicate the presence of both rneso-(lO) and dl-forms (1 1).
Ph-P-P-Ph
H H
Ph-P-P-Ph
Bonds to Boron.-Microwave spectroscopy of phosphineborane, H,PBH,,

and a number of isotopically labelled species indicates a staggered conformation with the following parameters:292
d(B-H)
= 1.212(2) A,
LBPH = 116.9(2)",
d(P-H)
= 1.399(3) A,
LPBH = 103.6(2)"
d(B-P)
= 1.937(5) A,
LHBH = 114.6(2)",
LHPH = 101.3(2)'
A dipole moment of 4.00(3)D was calculated and the barrier to internal rotation assessed at 2.47(5) kcal mol-l. The relationship between B-P bond
length and the stability of the borane adduct is also discussed.
1.r. and Raman data for H3P,BC13and D,P,BCl, at -196 OC were interpreted on the basis of CSvsymmetry,and a normal-co-ordinate analysisgave a
value of 1.96 mdyn A-1 for the P-B force constant.2s3In the adduct with
Me,P, the force constant was evaluatedas4as 2.37 mdyn A-l. Vibrational data
show that theH,P, BC1,adduct is dissociated at 0 "C, and this is supported by
lH n.m.r. data in the temperature range between -70 "C and room temperat ~ r e Changes
. ~ ~ ~in d,, and .IPHare consistent with an equilibrium between
the complex and its components, and averaging of the signals due to free
phosphine and the adduct. Signals due to H,P,BBr,, H,P,BBr,I, H,P,BBrI,,
and H,P,BI, were observed when PH, was treated with an equimolar mixture
of BBr, and BI, though appreciable halogen exchange occurs before adduct
290
291
292
2D3
a04
M. Baudler and D. Niemann, Naturwiss., 1973, 60, 389.

J. P. Albrand and D. Gagnaire, J. Amer. Chem. SOC.,
1972,94, 8630.
J. R. Durig, Y. S. Li, L. A. Carreira, and J. D. Odom, J. Amer. Chern. SOC.,1973, 95,
2491.
J. D. Odom, S. Riethmiller, J. D. Witt, and J. R. Durig, Znorg. Chem., 1973, 12,
1123.
J. D . Odom, B. A. Hudgens, and J. R. Durig, J. Phys. Chem., 1973,77,1972.
J. E. Drake and B. Rapp, J.C.S. Dalton, 1972, 2341.
Elements of Group V
471
formation. Parallel studies are reported for mixed boron halide adducts with
the stronger Lewis base CD,PH,.
Two thiophosphines, (MeS)PF, and (MeS),PF, and their borane adducts
have been prepared and chara~terized,,~~
and by a series of displacement
reactions the following order of base strength toward borane has been
established: MePF, > Me,NPF, > MeOPF, > MeSPF, 2 (MeS),PF. Although the value of JBpis generally in the same order, the high basicity of
MePF, is not mirrored by a large value for JBpin the adduct.
A r e - e ~ a m i n a t i o nof~ the
~ ~ n.m.r. spectrum of the adduct F,PPF,,BH, over
an extended temperature range shows that P-B coupling in the llB spectrum
appears on warming to -30 O C and is evident on each of the quartet components at 0 'C.The disappearance of coupling on cooling is thus not due to
rapid exchange of the BH, group but can probably be attributed to rapid
spin-lattice relaxation,
Changes in the B-H stretching frequency of borane-phosphite adducts
have been correlated with basicity of the phosphite and stability of the
a d d ~ c t , and
2 ~ ~in six-memberedcyclic phosphites such i.r. data show enhanced
basicity for axial lone pairs.299(Further information on borane adducts can
be found in refs. 353, 354,386,452, and 497).
Complex formation between MQP and the mixed halogenoboranes
BH+,&,
where X = C1 or Br and y1 = 0-3, together with BHBrCl,
BBrCl,, and BBr,Cl, was examined by lH, 31P, and llB n.m.r.
The only parameter which appeared to correlate with the thermodynamic
stability of the adduct was the chemical shift of the methyl protons on the
phosphine.
Reaction between either phosphine or PH41and BI, in carbon disulphide or
benzene solution gives H3P,B13,301which shows the B-P stretching mode in
the i.r. at 500 and 487 cm-l for the loB and llB isotopes, respectively.
X-Ray diffraction data indicate that the diborane(4) adduct B2H4,2PPh,is
centrosymmetric with the central, ethane-like, B,H4P, moiety in the anticonformation.302The B-B distance is 1.76 A and P-B is 1.94 A. The latter
bond is longer than that in the isostructural 2PF3,B,H4 adduct, which is less
stable. Molecular beam mass spectrometric experiments303have been carried
out on F,P,B,H, and Me,NPF,,B,H, in an attempt to observe the reactive
intermediate B,H,. Thermal decomposition of the latter complex, in fact,
gives a high-yield route to B,H, while at room temperature the adduct
decomposes to Me,NPF,,B,H,, which can be used as a route to B4H, itself.
The phosphine-bridged diborane (12)has been obtained in good yield by
2s6
297
290
300
301
302
303
R. Foester and K. Cohn, Inorg. Chem., 1972, 11,2590.

H. L. Hodges and R. W. Rudolph, Inorg. Chem., 1972, 11,2845.
D. W. White and J. G. Verkade, Phosphorus, 1973,3, 9.
D. W. White and J. G. Verkade, Phosphorus, 1973, 3, 15.
J.-P. Laussac, G. Jugie, J.-P. Lament, and F. Gallais, Cornpt. rend., 1973,276, C, 1497.
M. Schmidt and H. H. J. Schroder, Z . anorg. Chem., 1972,394,290.
W. VanDoorne, A. W. Cordes, and G. W. Hunt, Inorg. Chem., 1973,12,1686.
R. T. Paine, G. Sodeck, and F. E. Stafford, Inorg. Chem., 1972, 11, 2593.
472

treating H,P(BH,),Na with dry hydrogen chloride at low temperature, and
nmr. data rule out alternative structural formulae?o*CND0/2 calculations
(12)
(13)
on (12) and the isomeric bis(b0rane)phosphane (13) show the former to be

more stable, in agreement with experiment?O5 but on comparison with results
from ab initio calculations the CND0/2 method may give erroneous charge
distributions in the P-H bonds.
X-Ray data306are presented for the triclinic, a-modification, of the cyclic
phosphino-borine (Ph,PBH,),. The P3B3 ring has a chair conformation approaching C, symmetry) and the principal parameters are B-P 1.95 A;
B-H 1.11 A; LBPB 114.3'; LPBP 112.6'; and LCPC 103.1'. The B-P
distance is compatible with P -+B sigma-bonding only.
Bonds to Carbon.-Phosphorus(III) Compounds. Force constants) fcp =

9,100 mdyn A-1 andfcH = 6.250 mdyn A-1, have been calculated307from an
anharmonic force field for HCP. A simple preparative method for trimethylp h ~ s p h i n e ~involves
~*
the reaction between the trichloride and methyilithium in ether at -78 "C and gives yields of ca. 60%.
The deuteriated trifluoromethylphosphines CF3PD, and (CF&,PD result
in good yields from reactions of DI and mercury with, respectively, CF3PI,
and (CFd2PI;309the 19Fand 31P n.m.r. spectra show isotopic shifts when
compared with the hydrogen analogues. 1.r. and Raman spectra have been
measured and assigned for the deuterium and hydrogen compounds and
normal-co-ordinate analyses carried o ~ t ? Similar
~ ~ * preparative
~ ~ ~
and
vibrational data are given for the arsenic analogue^?^^-^^^ A detailed study312
has been made of molecular motions in phenylphosphine using data from the
temperature dependence of lH, 2H, and 31P relaxation times in PhPH,,
PhPD,, C6D5PH,, and C6D5PD,,and the lH n.m.r. spectra3130fthe methylene
groups in (PhCH,),PCOR (R = Me or CF,) can only be explained on the
basis of hindered inversion at the phosphorus atom.
H. Hofstotter and E. Mayer, Angew. Chem. Internat. Edn., 1973,12,413.
B. M. Rode and H. Hofstotter, Monatsh., 1973, 104, 1090.
306 G.J. Bullen and P. R. Mallinson, J.C.S. Dalton, 1973, 1295.
307 G.Strey and I. M. Mills, Mol. Phys., 1973,26, 129.
308 R.T. Markham, E. A. Dietz, jun., and D. R. Martin, J. Inorg. Nuclear Chem., 1973,
35, 2659.
309 R. Demuth and J. Grobe, J . Fluorine Chem., 1973,2,263.
310 H.Burger, J. Cichon, J. Grobe, and R. Demuth, Spectrochim. Acta, 1973,29A,47.
311 H.Burger, J. Cichon, R. Demuth, and J. Grobe, Specrrochim. Acru, 1973,29A,943.
31a S.J. Seymour and J. Jones, J. Magn. Resonance, 1972,8,376.
313 R.G.Kostyanovsky, Yu. I. Elnatanov, L. M. Zagurskaya, K. S. Zakharov, and A. A.
Fomichov, Bull. Acad. Sci. U.S.S.R., Div. Chem. Sci., 1972, 21, 1841.
304
Elements of Group V
473
Semi-empirical CNDO calculations314u
on PF,CN and PF, indicate that the
tramconfiguration is slightly (ca. 1 kcal mol-l) more stable than the cis, but
the authors have some reservations about this conclusion because of the
limited accuracy of the theoretical energy values. Considerable interaction
between phosphorus 3d orbitals and fluorine 2p orbitals is indicated. Positiveand negative-ion mass spectra have been reported for PF,CN.314bA harmonic
force field has been calculated315for P(CN), on the basis of previous vibrational
data and a corresponding analysis for As(CN), has led to a reassignment of
the vibrational frequencies. Cyanophosphine ligands (CF3)nP(CN),,, where
n = 0-2, obtained from CF,PI, or (CF,),PI and AgCN or Hg(CN), displace one carbon monoxide ligand from (NO)Co(C0),.3l6
New bisphosphino-acetylenes (R,N),PC i CP(NR,), and Me(R,N)PC i CP(NR,)Me have been obtained317 using the Grignard reagent
BrMgC i CMgBr and either (R2N),PC1 or Me(R,N)PCl. On treatment with
H,O,, sulphur, or selenium the compounds are oxidized to the respective
oxy-,thio-, or seleno-species. The tetra-amide gives (14) on treatment with
methyl iodide, and the unstable chloride C1,PC i CPCI, results with hydrogen
chloride. Preparative routes to a number of new polyphosphines (15)-(19)
[(R2N)2PMeC CPMe(NR2)2]2+21-
(14)
H2PCH2CH2PCH2CH2PCHzCHzPHa
Ph
Ph
(19)
containing combinations of primary, secondary, and tertiary phosphorus

atoms have been reported?l*
Vapour-phase Raman data for P,Me, suggest the presence of ca. 60%
gauche- and ca. 40% trans-isomer at ambient temperature.319
The M-P bond in the Group IV-phosphine derivatives R3MPH,, where
M = Si, Ge, or Sn, can be broken with bis(trifluoromethy1)halogenophosphines, (CF,),PX, to give the diphosphine (CF3),PPH,,320 while an alternative
314
315
316
317
318
319
320
( a ) W. R. Hall and H. F. Hameka, Inorg. Chem., 1973,12, 1878; (b) P. W. Harland,

D. W. H. Rankin, and J. C. J. Tliynne, ibid.,p . 1442.
S. J. Cyvin, S. K. Ratkje, V. Devarajan, V. V. Nayar, and G. Aruldhas, J. Mol.
Structure, 1973, 17, 317.
I. H. Sabherwal and A. B. Burg, Inorg. Chem., 1972, 11, 3138.
W. Kuchen and I(. Koch, Z . anorg. Chem., 1972, 394, 74.
R. R. King and J. C. Cloyd, jun., Z . Nuturforsch., 1972, 27b, 1432.
J. R. Durig and R. W. MacNamee, J . Mol. Structure, 1973, 17,426.
R. Demuth and J. Grobe, J . Fluorine Chem., 1973, 2 , 269.
474
route involves the reaction between (CF,),PX and LiAl(PH,),. The mixed
arsino-phosphine (CF3),AsPH2 can be obtained from Et,SiPH, and
(CF,),AsI, and routes are given to Me,AsPH,, Me,PPH,, and F,PPH,. Full
spectroscopic data are given for all the compounds. Vibrational data321for
(CF,),PPH, and the analogous arsenic compound are best interpreted on the
basis of only the trans-rotamer (C2J being present ; a normal-co-ordinate
analysis is given. The P-I? bond in the mixed diphosphine is readily cleaved
by both polar and non-polar
but with diborane and trimethylamine, addition products are formed. The new compounds CF,P(PH,),
and CF,As(PH,), can be prepared at 25 OC by reaction (5);322bthe products,
which are rapidly oxidized in air, were characterized by lH and 19F n.m.r.
spectroscopy.
2R3SiPH2 + CF3E12-+ 2R3SiI
CF3E(PH2),
(5)
E = P or As
1.r. and Raman data for (CF,),PP(CF,), show that in the gaseous and liquid
states two conformers, probably the trans- and gauche-forms, are present but
only the C,, (trans) form is present in the solid
The diphosphine
with W(CO), on heating to 175 "C to give a small yield of a doubly
bridged species (20), but the major volatile product is a liquid, W(CO)5[P(CF,),F], which arises by a novel fluorine-transfer process.
lH n.m.r. spectra of both Me,P, and MePhPPPhMe undergo dramatic

changes when dichloromethane or other solvents of high dielectric constant
are added to the pure
Similar effects do not occur with the unsymmetrical diphosphine Ph,PPMe, and the results are consistent with intermolecular association of the symmetrical diphosphines to give dimers such as
(21) or the analogous trimers.
A compound with the stoicheiometry Ph4P4S,originally obtained by the
reaction of sulphur with Ph,P5, can also be prepared from PhPCl, and potassium ~ulphide.5,~
The structure, elucidated by X-ray diffraction, contains a
321
322
323
s24
326
H. Burger, J. Cichon, R. Demuth, J. Grobe, and F. Hofler, 2. anorg. Chem., 1973,

396, 199.
R. Demuth and J. Grobe, ( a ) J. Fluorine Chem., 1973, 2, 299; (6) 2. Naturforsch.,
1973, 28b, 219.
( a ) J. D. Witt, J. W. Thompson, and J. R. Durig, Znorg. Chem., 1973, 12, 811; (b)
R. C. Dobbie, Znorg. Nuclear Chem. Letters, 1973, 9, 191.
H. C. E. McFarlane and W. McFarlane, J.C.S. Chem. Comm., 1972, 1189.
H. R. Calhoun, M. R. LeGeyt, N. L. Paddock, and J. Trotter, J.C.S. Chem. Comm.
1973, 623.
Elements of Group V
475
non-planar P4S ring system with phenyl groups alternately above and below
the mean ring plane. Metallation of Ph,P5 gives K2P3Ph3,which on treatment
with iodine at -78 "C is converted into triphenylcyclotriphosphane, a
derivative of P3H3.326aSimilar reactions occur in the presence of tetrahydrofuran, giving K2(PhP)31,,THF which decomposes in solution, liberating the
triphosphane. The compound is stable at -20 O C but rearranges to the more
stable Ph,P,, especially at higher temperatures. New carbon-phosphorus
cyclic systems (22)326band (23)326chave been prepared. The formerresults when
Hz
HZC-
Ha
PhPI 7
PPh
Phfc\rh
PhP-PPh
I I
PhP,
PhP PPh
,PPh
\J
Ph
C
Ha
\c'
C22)
(23)
(24)
Hz
1,2-dichloroethane reacts with the dipotassium salt of triphenylcyclotriphosphane, and the latter can be obtained from (24) by treatment with
potassium in tetrahydrofuran and dichloromethane.
Phosphorus(v) Compounds. A new cyclic tetraphosphonic acid with the
stoicheiometry C,H,,P3012 can be prepared by heating phosphorous acid and
acetyl chloride in a sealed tube at 120 oC?27a
Three acid dissociation constants
can be determined and the compound can be obtained as either a tri- or
tetra-hydate. N.m.r. and single-crystal X-ray studies on the hydrated calcium
salt show that the compound has structure (25).327b
The anion C4H,P,0:; is a
H3C,
,P(o)(oH)z
n
(251
326
337
( a ) M. Baudler and M. Bock, 2. anorg. Chem., 1973, 395, 37; (b) M. Baudler, J.
Vesper, and H. Sandmann, 2. Naturforsch., 1972, 27b, 1007; (c) M. Baudler, J.
Vesper, and H . Sandmann, ibid., 1973, 28b, 224.
(a) G . Brun and C. Blanchard, Rev. Chim. minbrale, 1972, 9 , 4 5 3 ; (6) E. Phillippot,
G. Brun, J . 4 . Dumas, and M. Maurin, Rev. Chim. mindrule, 1972,9,591.
Inorganic Chemistry of the Muin-group Elements
476
centrosymmetric six-membered heterocycle in the chair conformation with

the following parameters: P-0 = 1.618(3), P-C = 1.854(4), and C-0 =
1.449(3) A; the exocyclic P-0 distances are 1.484 and 1.497 A. The heterocycles are connected by hydrogen bonds from an acid function, giving
0 - * 0 distances of 2.507 A.
1-Hydroxyalkyl-1,l-bis(a1kylphosphinic acids) can be prepared from reactions such as:328
0 R2 0
2R1PH(0)(OH)
R1 =
MeorEt
R2COCl
R2
II
I
R'-P-C-P-R'
MeorEt
II
l
OHOHOH
Treatment with PCl, replaces the three hydroxy-groups by chlorine, and the
resulting chloroalkylbis(alky1 phosphinic chlorides) (26) can be hydrolysed
to l-chloroalkylbis(phosphinic acids) (27).
When white phosphorus reacts with formaldehyde in the presence of

sodium hydroxide the product is a mixture of HOCH,P:O(OH),,
(HOCH,),PO(OH), and CH,(HOCH,)PO(OH).329 Although separation of
the mixture was not possible, three products, ClCH,POCI,, (ClCH2),POCI,
and Me(ClCH,)POCI, were isolated and identified after chlorination with
thionyl chloride. 1.r. spectra"30of the disodium salt of hydroxymethylphosphonic acid, HOCH2P03Na2,obtained over a temperature range down to
- 180 "C, have been assigned paying particular attention to hydrogen-bond
formation involving the hydroxy-group.
Phenylphosphonates and 1-phenylvinylphosphonates of a number of rareearth elements have been isolated and characterized by solubility and i.r.
meas~rements3~~
The phenylphosphonates have the formula Ln,(C6H5P03),
but both neutral and acid Ln[C6H5C(P03H)CH,], series are known for the
vinyl derivatives. Resolution of O-methyl isopropylphosphonothioic acid
(28) into its optical isomers has been achieved by fractionation of its salts
S
Me
'CH-P-OH
Me
328
32B
330
331
II
OMe
K.-H. Worms and H. Kranz, 2. anorg. Chem., 1973, 399, 1.

L. Maier, Z . anorg. Chem., 1972, 394, 117.
G. Brun and G. Jourdan, Compr. rend., 1972, 275, C, 821.
V. N. Biryulina and V. V. Serebrennikov, J . Gen. Chem. (U.S.S.R.),1972,42, 1682.
Elements of Group V
477
with a-phenylethylamine or e ~ h e d r i n e . 3A~ new
~ process is described333for
preparing 2-alkoxyvinyl phosphonates (29) by splitting off an alcohol (ROH)
from a phosphono-substituted acetaldehyde acetal (30).
ROCH=CHP(O)(OEt)3
(R0)2CH-CI2-P(O)(OE
t)z
Crystallographic data indicate that tetramethylformamidinium phosphonic

anhydride (3 1), prepared from triethyl phosphate and tetramethylformamidinium chloride, is a double inner ~ a l t . 3 The
~ " molecule has a crystallographic
(3 1)
two-fold axis through the bridging oxygen atom and a feature of interest is a
C-P bond linking atoms carrying opposite charges. Bond distances are:
P-0 (terminal) 1.469 A; P-0 (bridge) 1.619 A; N-C 1.331 A; and P-C
1.880 A. The POP bridge angle (125.9") is smaller than that found in the
diphosphate anion, and the PC(NMe,), groups are not planar. Methylenediphosphonic acid, (HO),(O)PCH,P(O)(OH),, has a structure334bwhich
deviates from an eclipsed conformation by ca. 30' when viewed along the
P-P vector. The F-C bond lengths are 1.790(3) and 1.794(3) A and the
PCP angle is 117.2(1)"; P-0 bond lengths are 1.494(2) and 1.500(2) 8,while
the average P--O(H) length is 1.546 A. Each of the oxygen atoms in the
former bonds is an acceptor for two hydrogen bonds.
A review on low molecular weight polyphosphonates, e.g.
I
1
R~O~P-C-PO~RZ and R2O3P--C-C-PO3R2
has been p ~ b l i s h e d . 3Intermediates

~~
such as (32)-(35) have been isolated
in the reaction between phosphorus(II1) compounds and acetylating agents.336
The final product is ethane-l-hydroxy-1,l-diphosphonic acid (36) and the
intermediates are condensation products of this compound. The presence of
three further compounds is inferred from 31Pn.m.r. data. An ethene-diphosphonate (37) can be obtained by the nickel-chloride-modified Arbuzov
332
333
334
335
388
M. Mikolajczyk and J. Omelahczuk, Phosphorus, 1973, 3,47.

L. Maier, 2. anorg. Chem., 1972, 394, 111.
(a) F. Sanz and J. J. Daly, J.C.S. Dalton, 1972, 2267; (b) D. DeLaMatter, J. J.
McCullough, and C. Calvo, J . Phys. Chem., 1973, 77, 1146.
J. D. Curry, D. A. Nicholson, and 0. T. Quimby, 'Topics in Phosphorus Chemistry',
ed. E. J. Griffith and M. Grayson, Interscience, New York, 1972, Vol. 7, p. 37.
J. B. Prentice, 0. T. Quimby, R. J. Grabenstetter, and D. A. Nicholson, J. Amer.
Chem. Soc., 1972, 94,6119.
478
n = Oandn = 2-4
(32)
0-
? P
HO-P-0-P-OH
I
I
0tP-0-P+0
H3CLI
I
CHj
AcO/F
Y<OAo
OtP-O--P-+O
H203P-C-O-C-PO3H2
CHj
CB3
0-
0(33)
0-
0-
(34)
0-
I
I
I
I
HaC-C-0-C-CHS
I
I
OtP-O-P~O
I
I
0tP-O-P-+O
0-
PO3-
HSC-C-OH
Po: -
0-
(36)
(35)
reaction of 1,Zdichloroethylene and triethyl ph0sphite,3~~"

while a chlorinesubstituted compound results if 1,1,2-trichloroethyleneis used. Both products
have trans-structures and hydrolysis gives the sodium salt of the half ester,
which can be converted into the acid by ion exchange. A number of reactions,
e.g. epoxidation, chlorination, of the compound are described.
A 1,2-dicarboxy-derivativeof (37) has been prepared by dehydrogenation
of dimethyl tetraethyl ethane-l,2-dicarboxy-l ,Zdiphosphonate (38),537band
its sequestering action has been tested. A monophosphonate analogue (39)
(Et0)2P-CH=CH-P(
II
II
OEt),
0
(37)
H H
I I
Me02C-~-~-C02Me
MeOzC
'c=c
/
Me203P
537
/H
'COeMe
(a) L. Maier, Phosphorus, 1973, 3, 19;
(b) D. A. Nicholson, ibid., 1972, 2, 143.
Elements of Group V
479
results when dimethyl hydrogen phosphite is added to dimethyl acetylenedicarboxylate; n.m.r. spectroscopy shows that a greater amount of the cisform is present.
Isobutylene is eliminated when t-butylaminomethylphosphonic acid,
ButNHCH2P(O)(0H),, is heated in a sealed tube with concentrated hydrochloric acid, giving a high yield of aminomethylphosphonic acid,
H2NCH2P(0)(OH)2;33sa
a similar reaction with simultaneous ester hydrolysis
occurs with ButN [CH,P(O)(OEt),],, providing an easy route to iminodimethylene diphosphonic a ~ i d . 3 ~ ~ ~
Molecules of diphenylphosphinicacid, Ph,P(O)OH, are linked together by
hydrogen bonds [O-H * * - 0 distance 2.468(8) A] to form chains, according
to a recent structure determinati0n.3~~
The P-0 distances are 1.486(6) and
1.526(6)A and the OPO and CPC angles are 116.6(3)" and 107.7(3)',
respectively. Methods for preparing the trimethylsilyl esters of phosphinic
acids, R,P(O)OSiMe,, where R = Me, Et, or But, together with the monoand di-thio-analogues are discu~sed.3~~
A number of reactions are described,
including that between arsenic trichloride and the dithio-compounds to give
[R,P(S)S],As. Vibrational spectroscopic data for Me,P(O)SMe, Me,P(S)SMe, MeP(O)(SMe),, and MeP(S)(SMe), have been a n a l y ~ e d and
~ ~ l force
constants calculated on the basis of a simplified valence force field.
Ligands based on structure (40), where R1 = R2 = Me, X = 0 or S;
R1 = R2 = Ph, X = CH,, 0, or S ; R1 = Me, R2 = Ph, X = CH,, 0, or S ,
RiP-X-PR!
sII
(40)
have been synthesized for reaction with 'class b' metal halides.3421 :1 Complexes M(chelate)Cl, are obtained except when R1 = R2 = Ph and X = 0,
and i.r. evidence indicates that bonding is uiu the P-S groups. For the ligand
with R1 = R2 = Me and X = S , cleavage occurs and phosphinodithionate
complexes result .
The ylide Me,P:CH, reacts with methanol and ethanol to give the fiveco-ordinate species Me4POMe and Me,POEt ,343 which from variabletemperature 31P and l H n.m.r. data are considered to contain an alkyl group
in an axial position. On heating the products to ca. 130C an alkane is
eliminated, with the formation of trimethylphosphine oxide.
Bonds to Silicon, Germanium, or Tin.-Experiments

in the presence of
Me2SiD, show that the thermal decomposition of ~ilylphosphine~~~
follows
338
339
340
341
3ga
843
344
(a) K. Moedritzer, Synth. Inorg. Metal.-org. Chem., 1972, 2, 317; (b) K. Moedritzer,
ibid., 1973, 3, 75.
D. Fenske, R. Mattes, J. Lons, and K.-F. Tebbe, Chem. Ber., 1973, 106, 1139.
H. Steinberger and W. Kiichen, 2. Naturforsch., 1973, 28b, 44.
R. Pantzer, W. Schmidt, and J. Goubeau, Z. anorg. Chem., 1973, 395, 262.
D. A. Wheatland, C. H. Clapp, and R.W. Waldron, Inorg. Chem., 1972, 11, 2340.
H. Schmidbaur, H. Stuhler, and W. Buchner, Chem. Ber., 1973, 106, 1238.
L. E. Elliott, P. Estacio, and M. A. Ring, Inorg. Chem., 1973, 12, 2193.
480
the two steps:
+ SiHz + PHs
SiHsPH2 + SiH4 + PH
SiH3PH2
The biradicals then insert into the Si-D bonds to give, respectively,
Me2Si,H2D, and Me,SiPHD,.
Mixed compounds with the formula Me,ME(CF,),, where M = Si, Ge,
or Sn and E = P or As, can be obtained in good yield from reactions between
Me,MPH, and HE(CF3)2?45aThe rate of reaction depends on both M and E,
increasing in the order Si < Ge < Sn and P < As. The compounds were
characterized by full n.m.r. and i.r. measurements, and reactions involving
bond cleavage, etc. are described. Similar compounds with formulae such as
M%GePH(CF3), Me,SnPH(CF,), and (Me3Ge),PCF3 and the arsenic
analogues have also been described.35b
Germyl- and silyl-ph~sphines~~~
add readily to one of the carbonyl groups
of glyoxal to give unstable products which readily lose carbon monoxide, e.g.
RSMPEt,
(CH0)2*
M = Si or Ge
R3MOCHCH0
-"
R3MOCHzPEtz
PEtz
With Me,Si(PEt,),, on the other hand, glyoxal gave the cyclic species (41)
but the analogous germanium compound is apparently unstable and only
R,Ge (OCH2PEt2),was isolated.
Bonds to Halogens.--Phosp~orus(rIr) Halides. 31P and 19Fn.m.r. measurements%' on PF, in a nematic solvent [N-(p-ethoxybenzy1idene)y-butylaniline]
were used to calculate the molecular geometry, which is in agreement with
microwave and electron-diffraction results. Dipole moments, shown in
parentheses, were obtained348by a gas-phase heterodyne beat method for
PF, (1.00 f 0.03 D), PF,Cl(O.93 f 0.01 D), PFCl, (0.86 f 0.05 D), PF2Br
(0.83 f 0.05 D), and PF21 (0.085 f 0.06 D). The values agree reasonably
with the vector sums of the P-X moments.
347
(a)S. Ansari, J. Grobe, and P. Schmid, J . Fluorine Chem., 1953,2,281; (6) S. Ansari
and J. Grobe, Z . Naturforsch., 1972, 27b, 1416.
C. Couret, J. SatgC, and F. Couret, Inorg. Chem., 1972, 11, 2274.
N. Zumbulyadis and B. P. Dailey, Mol. Ph-ys., 1973, 26, 777.
348
J. G. Morse and R. W. Parry, J . Chem. Phys., 1972, 57, 5372.
346
346
Elements of Group V
48 1
A review on vibrational and n.m.r. spectroscopy of compounds containing

phosphorus-fluorine bonds has been p u b l i ~ h e d The
. ~ ~ chemistry of phosphorus(@ fluorides and their co-ordination compounds has been briefly
reviewed,350and rearrangements of the five-co-ordinate PF,-transition-metal
hydride species HM(PF3)4 (M = Co, Rh, or Ir) and [HM(PF,),]- (M =
Fe, Ru, or Os), together with M(PF& (M = Fe, Ru, or 0s) have been
st~died.35~
Phosphorus trifluoride is readily oxidized to PXF, (X = 0, S, or Se) when
treated with the free element at pressures up to 4000 atm and temperatures in
the region of 300 0C?52The selenium compound is light-sensitiveand decomposes at room temperature to red selenium and PF,. Tellurium did not react
with PF, under these conditions.
Difluorophosphites PF,OR, where R = Me, Et, or CF,CH,, can be obtained353directly from PF, and the appropriate alcohol in the presence of
pyridine. Borane adducts can be prepared, and displacement reactions indicate decreasing base strength in the order OEt > OMe > OCH,CF,. The
monohydride PF,H, when treated with methanol and pyridine, gives dimethoxyphosphine, (MeO),PH, which can also be prepared by reducing
(MeO),PCl with tributyltin h~dride.,~*
The compound was fully characterized
and the borane adduct prepared. Pentaco-ordinate species (42), which are
p
A-P
I bH-
F
(42) A = OMe, OEt, SMe, or SEt
intermediates in the PF,H reactions with alcohols and thiols, have been isolated,355and n.m.r. spectroscopy at -60 O C shows that the fluorine atoms are
in axial positions.
The results of ab initio SCF-MO calculations356for PFzH and OPF,H
both with and without inclusion of phosphorus d-orbitals have been compared
with data for PF,, OPF,, PH,, and OPH,. The electronic structure and conformation of H,PPF, have been investigated by the CND0/2 approximati0n.3~ New absorption and flash photolysis data358which disagree with
previous results have been obtained for PF,H, P2F4,PF,Cl, and PFCl,. 1.r.
349
350
351
352
353
364
355
356
367
358
H.-G. Horn, Chem.-Ztg., 1972, 96, 666.

J. F. Nixon, Endeavour, 1973, 32, 19.
P. Meakin, E. L. Muetterties, and J. P. Jesson, J. Amer. Chem. Soc., 1972, 94, 5271.
A. P. Hagen and E. A. Elphingstone, Inorg. Chem., 1973, 12,478.
E. L. Lines and L. F. Centofanti, Inorg. Chem., 1973, 12, 2111.
L. F. Centofanti, Inorg. Chem., 1973, 12, 1 1 3 1 .
L. F. Centofanti and R. W. Parry, Inorg. Chem., 1973, 12, 1456.
I. Absar and J. R. Van Wazer, J . Amer. Chem. SOC.,1972, 94, 6294.
M.-C. Bach, F. Crasnier, J.-F. Labarre, and C. Leibovici, J . Mol. Structure, 1972,
13, 171.
E. G. Skolnik, R. J. Salesi, C. R. Russ, and P. C. Goodfriend, J. P h p . Chem., 1973,
77, 1126.
482
and Raman datas9 for P2F4 in the solid, liquid, and gas phases strongly
indicate a trans (C2J structure; there is no evidence for thegauche rotamer or
other structures of low symmetry.
Both phosphorus-(111) and -(v) nitroxide fluorides result360when halogenophosphines or halogenophosphoryl compounds react under carefully controlled conditions with either (CF3),N0 or Hg[ON(CF,),],. Species such as
(CF3)2NOPF2 1(CFd2NO12PF3, [ ( C F ~ ) ~ N O ] Band
~ F ~(CF3)2NOP(O)F2
have been isolated and characterized. On heating at 70 "G for one hour,
(CF3)2NOPF2isomerizes to (CF3),NP(0)F2.
Reduction of PCl, with hydrogen in the temperature range 150-800 O C to
give P4 and HCl has been
and a gas-phase activation energy of
25.6 kcal mol-l is reported for the process. 35Cl n.q.r. measurements for
phosphorus(1n) chlorides XPC12 (X = alkyl, RS, RO, or R2N) and XYPCl
(X and Y = alkyl, OCH2CH20,R2N, etc.) show that the resonance position
depends markedly on the mesomeric effect of the X and Y
Two
signals for R2NPClz indicate non-equivalence of the chlorine atoms, and
similarly two 14Nn.q.r. signals are found for (R,N),PCl.
Phusphorus(v) Halides. Possible modes of rearrangement for trigonalbipyramidal phosphoranes have been analy~ed:~, and the contribution of
d-orbitals to a- and v-bonding in Main-group elements has been reviewed.364
The d-orbitals on phosphorus play an important role in the electronic structure of PF, through d,-p, bonding according to an ab initio LCAO-MO-SCF
c a l ~ u l a t i o n The
. ~ ~ approach accounts for the different P-F bond lengths
and supports the Berry pseudorotation mechanism for ligand interchange.
Molecular vibrations in PF, and other trigonal-bipyramidal molecules have
been studied using the electron-pair-repulsion approach (Gillespie-Nyholm
showing that pseudorotational barriers can be related to force
constants.
X-Ray photoelectron spectroscopy367of PF, shows asymmetry in the F(1s)
peak, in agreement with the presence of two different types of fluorine atom.
The shape is consistent with the two axial fluorines being more negatively
charged than the equatorial atoms. Similar experiments with SF, and ClF,
show in each case two separate F(1s) peaks. New P-F stretching force
constants have been estimated368 from bond-polarizability derivatives
358
360
362
363
364
365
366
368
K. H . Ree, A. M. Snider, jun., and F. A. Miller, Spectrochim. Acta, 1973,29A, 1029.

C. S. Wang and J. M. Shreeve, Inorg. Chem., 1973,12,81.
B. A. Savel'ev, V. A. Krenev, and V. I. Evdokinov, R u n . J. Inorg. Chem., 1972, 17,
1368.
D. Ya. Osokin, I. Ya. Safin, and I. A. Nuretdinov, Bull. Acad. Sci. U.S.S.R.,Div.
Chem. Sci., 1972,21, 1460.
J. I. Musher, J . Amer. Chem. SOC.,
1972, 94, 5662.
T. B. Brill, J . Chem. Edirc., 1973, 50, 392.
A. Strich and A. Veillard, J. Amer. Chem. SOC.,1973, 95, 5574.
L. S. Bartell and V. P. Iato, J . Amer. Chem. SOC.,1973, 95, 3097
R. W. Shaw, jun., T. X. Caroll, and T. D. Thomas, J . Amer. Chem. Soc., 1973, 95,
2033, 5870.
R. S. Gay, B. Fontal, and T. G. Spiro, Znorg. Chem., 1973,12, 1881.
Elements of Group V
483
obtained from Raman intensities of the symmetric vibrational modes of PF,.
The lowest energy fundamental frequency of PF, has been estimated to occur
at 166 f 15 cm-19369 and transitions of the PF diatomic have been observed370
in the afterglow produced when PF, with an inert gas is pumped through a
microwave discharge.
Slight traces of moisture or HF can markedly affect the n.m.r. spectra of
compounds such as PF,, RPF,, etc., but great improvements are noted on
addition of a small amount of MqSiNEt,, which reacts with both impuriOn the basis of vibrational spectroscopy, the 1 : 3 adduct between
PF, and SbF, is formulated as PFpf Sb3FG.371b
A convenient synthetic method372for HPF, involves the gas-phase reaction
of PF, with Me,SiH, and IH and 19Fn.m.r. spectra on solutions in HCCIF,
clearly establish a structure based on a trigonal bipyramid with two axial
and two equatorial fluorine atoms. Complete analysis of i.r. and Raman
data373supports a similar structure for the gas phase, and data for H2PFs
indicate a C,,structure with two equatorial hydrogen atoms.
Detailed vibrational spectroscopy on crystalline ammonium hexafluorophosphate374confirms phase transitions at ca. 190 and 130 K, and possible
structures are discussed. The presence of appreciable amounts of HF in the
hexahydrate of HPF, is shown by recent n.m.r.
and the
compound should be formulated as H30+PF;,HF,4H20. Each of the species,
H20, H,Of, and HF, participates fully in a four-co-ordinate scheme of
hydrogen-bonding to give the truncated octahedral cage shown in Figure 8.
A re-examination of the 35Cl n.q.r. of PCI5 below the transition point at
102 K shows that all ten chlorine atoms (PClh PCl;) are crystallographically
non-equivalent,376and temperature-dependence studies suggest that there is a
change in the orientation of the PCI; ion. Heat-capacity measurements377
over the range 4-150 K lend support to this explanation. Information from
Raman spectroscopy and freezing-point measurements378imply that in solvents such as acetonitrile, nitromethane, and nitrobenzene, PCI, is involved
in the two competing equilibria:
+ Pap+ + PCI,
PCls + Pa: + c1-
2PCIb
369
370
371
374
373
374
375
376
377
378
32
J. Schatz and S. Reichman, J . Chem. Phys., 1972, 57,4571.

R. Collin, J. Devillers, and F. Prevot, J. Mol. Spectroscopy, 1972, 44, 230.
(a) A. F. Janzen, J. A. Gibson and D. G. Ibbott, Inorg. Chem., 1972, 11, 2853; (6)
G. S. H. Chen and J. Passmore, J.C.S. Chem. Comm., 1973, 559.
A. H. Cowley and R. W. Braun, Inorg. Chem., 1973,12,491.
R . R. Holmes and C. J. Hora, jun., Inorg. Chem., 1972, 11, 2506.
A. M. Heyns and G. J. Van Schalkwyk, Spectrochim. Acta, 1973, 29A, 1163.
D. W. Davidson and S. K. Garg, Canad. J . Chem., 1972,50,3515.
H. Chihara and N. Nakumara, Bull. Chem. SOC.Japan, 1973,46,94.
H. Chihara, N. Nakumara, and K. Masukane, Bull. Chem. SOC.Japan, 1973,46, 97.
R. W. Suter, H. C. Knachel, V. P. Petro, J. H. Howatson, and S. G. Shore, J. Amer.
Chem. Soc., 1973,95, 1474.
484
Figure 8 m e truncated octahedral cage of HPF6 hydrate

(Reproduced by permission from Canad. J . Chern., 1972,50,3515)
Above ca. 0.03 mol l-l, the first is predominant but at lower concentrations
the second is more important. Freezing-point studies in benzene and carbon
tetrachloride are interpreted as showing the formation of solid solutions in
the latter, and when allowance is made for this, the molecular weight of
PCl, is no longer anomalous and is in good agreement with that for the
monomer.
The presence of the PCli cation with almost perfect tetrahedral geometry
(P-Cl = 1.925 .$) is revealed by a crystal-structure determination of the
1 : 1 compound PC1,,TeC1,.379 The anion is a polymeric (TeCl;), chain which
is best described in terms of TeCl, groups with C,, symmetry which are
linked by two additional chlorine atoms in cis-positions. A crystalline compound Cl,F,PS, of unknown structure, results from the reaction between
SF, and either PCl,, POCl,, or Pel, under pressure at 150 0C.380
The mixed halide PBr,Cl can be prepared381from a 4: 3 mixture of PCl,
and PBr, and recrystallized from carbon disulphide; X-ray powder diffraction
data show that it is isomorphous with PBr,, and the compound is best considered as PBriCl-. Ligand-exchangereactions between equilibrated mixtures
of PCl,ICl, and PBr,IBr, have been observed by 31Pn.m.r. spectroscopy, and
the existence of mixed cations with the formula [PCl,Br4-,]+, 0 Q n Q 4,
is confirmed.38231P n.m.r. data have also been obtained for these species in
liquid hydrogen chloride solution.?83
379
380
381
382
383
B. Krebs, B. Buss, and W. Berger, Z . anorg. Chem., 1973,397,l.

L. N. Markovskii, E. A. Stukalo, and A. V. Kirsanov, J . Gen. Chem. (U.S.S.R.),
1972, 42,2514.
W. Gabes, K. Olie, and H. Gerding, Rec. Trav. chim., 1972, 91, 1367.
A.-R. Grimmer, Z . anorg. Chem., 1913, 400, 105.
K. B. Dillon, T. C. Waddington, and D. Younger, Inorg. Nuclear Chern.Leffers,1973,
9,63.
Elements of Group V
485
Compounds containing P-C Bonds. Vibrational data for CF,PX,, X =
halogen or hydrogen, have been assigned3s4on the basis of C,symmetry but
there is considerable mixing of the internal co-ordinates of vibration, and
simple group-frequency correlations cannot be made for all bands.
Reactions between t-butyl chloride, methyldichlorophosphine, and metal
chlorides such as NbCl,, TaCl,, and wc16 give air- and water sensitive compounds of the type [ButMePC1,][MVC1,], while with phosphorus trichloride
in place of MePCl, the analogous [ButPC13][MVC16]
compounds are formed.385
Vibrational data and magnetic measurements support the structures proposed
when PF,Br is treated with LiC,H, to give prop-1-ynyldifluorophosphine
H,CC:CPF,,386 and although the compound forms a BH, adduct, attempts
to form a BCl, compound led to the isolation of C,H,PF, as the only volatile
product. The tetrafluoride can also be obtained by either thermal decomposition of the difluoride or by allowing the difluoride to react with antimony
trifluoride.
Hindered rotation about the P-C bond is indicated in a recent electronThe reaction of the chlorodiffraction study of phenyldichlor~phosphine.~~~
phosphines RPCl, and R,PCl with trifluoroacetic acid gives the unstable
n = 1 or 2, R = Et or Ph.388 On
acetoxy-derivatives R,P(OCOCF,),,,
heating, the monoethyl compound loses trifluoroacetic anhydride and carbon
monoxide, i.e.
0
2EtP(OCO*CF&
--(cF3c0)20+
II
II
Et-P-0-P-Et
I
I
0
-*'O
II
+ Et-P-0-F-Et
11
I
and although the phenyl analogue gives a similar final product,

PhP(O)(COCF,), is an intermediate here. The final products from the diethyl and diphenyl derivatives are phosphinic acid anhydrides with formulae
R2P(0)0P(CF3)2R2*
A number of routes to the trimethylsilyl esters of phosphinous and thiophosphinous acids have been investigated389and although compounds with
the formulae F,POSiMe,, (CF3),POSiMe3, and (CF,),PSSiMe, can be obtained, it appears that F2PSSiMe, is thermally unstable. Attempts to prepare
the phosphorus(v) isomers, i.e. F,P(O)SiMe, and F,P(S)SiMe,, were unsuccessful and, as only the phosphorus(II1) forms were obtained, it is concluded that the phosphorus(v) isomers are susceptible to anti-Arbuzov
rearrangements. Reactions with dimethylamine are complicated but with
384
385
386
387
388
389
J. D. Brown, R. C. Dobbie, and B. P. Straughan, J.C.S. Dalton, 1973,1691.

J. I. Bullock, F. W. Parrett, and N. J. Taylor, J.C.S. Dalton, 1973, 522.
E. L. Lines and L. F. Centofanti, Inorg. Chem., 1973,12,598.
V. A. Naumov, N. M. Zapipov, and N. A. Gulyaeva, J . Struct. Chem., 1972,12,850.
P. Sartori and M. Thomzik, Z . anorg. Chem., 1972, 394, 157.
R. G. Cavell, R. D. Leary, A. R. Sanger, and A. J. Tomlinson, Inorg. Chem., 1973,
12, 1374.
486
(CF,),POSiMe,, CF3H is displaced giving CF,(Me,N)POSiMe,. The stability of the (CF,),PSSiMe, form has also been attributed to high m-bond energy
in the P-S-Si
system.39o
Good yields of MeP(CH,Cl)Cl and ClCH,PCl, can be obtained by treating
respectively methyldichlorophosphine or phosphorus trichloride with dichloromethane in the presence of aluminium trichloride and
while the simultaneous reaction of dichlorophosphineswith hydrogen fluoride
and water in ether gives derivatives of fluorophosphonous acid, RPH(O)F,
where R = Me, Et, or Ph.3921.r. and Raman spectra of B u ~ P Fand BuEPCl
are consistent with C,symmetry for the skeleton and local C,, symmetry for
the t-butyl g r o ~ p s . ~ ~ 3
Details are given in Inorganic Syntheses for the preparation of MePF4.394
Two of the fluorine atoms in PhPF, can be substituted in reactions with perfluorinated carboxylic acid a m i d e ~ , 3
~~
e.g.
PhPF4
RCONH2 -+ RCON=PF2Ph
R = CF30r C3F7
2HF
while with the hydrazide CF,CONHNMe,, the product is

,NMe2
PhPF3N
COCF3
A phosphoranyl pyrrole (43) has been prepared and a crystal-structure

determination is rep0rted.3~~
Greatly improved stability is reported for the monoalkoxyfluorophosphoranes R1PF3(OR2)when R2 is either isobutyl, neopentyl, or an electronattracting
The compounds are prepared by cleavage of the Si-0
bond in Me,SiOR2 with either MePF, or PhPF,, and low-temperature n.m.r.
390
391
392
393
394
395
398
SD7
K. Gosling and J. L. Miller, Inorg. Nuclear Chem. Letters, 1973, 9, 355.

M. Wieber and B. Eichhorn, Chem. Ber., 1973,106,2733.
U . Ahrens and H. Falius, Chem. Ber., 1972,105,3317.
R. R. Holmes, G. T. Fey, and R. H. Larkin, Spectrochim. Acta, 1973,29A, 665.
P. M. Treichel, J. Benedict, and R. G . Haines, Inorg. Synth., 1972, 13, 37.
G . Czieslik and 0. Glemser, 2. anorg. Chem., 1972, 394, 26.
M. J. C. Hewson, R. Schmutzler, and W. S. Sheldrick, J.C.S. Chem. Comm., 1973,
190.
D. U. Robert, G . N. Flatau, C . Demay, and J. G. Riess, J.C.S. Chem. Comm., 1972,
1127.
Elements of Group V
487
data show that two of the fluorine atoms occupy axial positions in a trigonalbipyramidal arrangement. 31P and 19F n.m.r. data are presented398for a
number of substituted acetylene phosphonic difluorides, e.g. RC :CPOFz
and
RC=CPOFz
Cl
c1
Primary and secondary amine derivatives of truns-l-chloro-2,2,3,4,4pentamethylphosphetan l-oxide (44)can be obtained399by heating the compound and the amine in toluene in a sealed tube to 215 "C. Detailed n.m.r.
and i.r. data for the products show evidence for hindered rotation around the
P-N bond, and some degree ofp,-d, bonding is considered to be a contributing factor. The diphosphonic anhydride (45) which results when (44)is
fe.
Me-
Me
-M
Me
(44)
hydrolysed at temperatures between 50 and 100 "C contains the most stable
P-0-P
linkage known.400
After 6oCo?-irradiation of PhPOCl, and PhPSCI,, e.s.r. signals characteristic of the corresponding radical anions were observed, while signals of lower
intensity could be assigned to PhP(0)CI and PhP(S)Cl radicals.401 On
annealing, the oxy-compound gave Cl; while the sulphur analogue in contrast gave PhPSCl radicals. Dimeric species resulting from processes such as:
PhPOC12^
+ PhPOClz
+ Cl2P-0-P=O
Ph
C1,
C1-
Ph
are also thought to be involved. Phenylthionophosphine oxide (46),prepared

from a reaction between PhPOCla and hydrogen sulphide in the presence of
triethylamine:02 is trimeric in solution and the solid-state, and X-ray diffraction data indicate the presence of a P,O, ring system which is almost planar.
The truns-isomer with two sulphur atoms and one phenyl group on one side of
the ring was obtained. Ethanol and diethylamine cleaved the ring, giving
3s8
39s
400
401
402
E. Fluck and N. Seng, 2. anorg. Chem., 1972,393, 126.

J. Emsley and J. K. Williams, J.C.S. Dalton, 1973, 1576.
J. Emsley, T. B. Middleton, J. K. Williams, and M. F. Crook, Phosphorus, 1973, 3,
45.
S. P. Mishra and M. C. R. Symons, J.C.S. Dalton, 1973, 1494.
J. J. Daly, L. Maier, and F. Sanz, Helu. Chim. Acta, 1972, 55, 1991.
488
lnorganic Chemistry of the Main-group Elements
(46)
PhP(S)(OH)(OEt) and PhP(S)(OH)(NEt,), respectively, while with water

phenylphosphonic acid was the product.
Two methylene-bridged phosphoryl fluorides, CH,(POF,), and CH,(COF)(POF2), have been prepared403by fluorinating the corresponding chlorides
with either antimony or arsenic trifluorides.
The Si-N bond in substituted piperidylsilanes is cleaved by phenylfluorophosphoranes Ph,PF,,,
n = 0-2, to form substituted piperidyl fluorophosphoranes (47),404 and trigonal-bipyramidal structures with the amino-
(47)
and phenyl groups in equatorial positions are suggested by 31Pn.m.r. measurements. 19Fn.m.r. data at room temperature indicate interchange of axial and
equatorial fluorines, but on cooling, the tetrafluorides of 2- and 3-methylpiperidine show non-equivalence of the two equatorial fluorines, probably as
a result of restricted rotation around the P-N bond. This effect is not observed in the 4-methyl derivative. A series of dithiaphospholes (48) can be
prepared by reaction (6), but with phenyl or methyl tetrafluorophosphane the
aSSiMe3
+ W'Fs-n
SSiMe3
R
R
W P R a 3 - .
'
= PhorMe,n = 2
= Pri,n = 3
+ 2MesSiF
(6)
s'
(48)
product is a spiro-derivative (49), and PF, itself gives the ionic compound
(50).*05 Single-crystal data for (49; R = Me) show that co-ordination about
403
40*
406
W. Althoff and M. Fild, 2.Nuturforsch., 1973, 28b, 98.

M. J. C. Hewson and R. Schmutzler, 2. Naturforsch., 1972, 27b, 879.
M. Eisenhut, R. Schmutzler, and W. S. Sheldrick, J.C.S. Chem. Comm., 1973, 144.
Elements of Group V
489
phosphorus is intermediate between trigonal-bipyramidal and squarepyramidal.
Strong evidence for intramolecular fluorine exchange in Ph,PF, has been
obtained406from 19F and 31P n.m.r. spectra in the temperature range 32170 "C. Silyl esters of bis(trifluoromethy1)- and difluoro-phosphinic acids and
their thio-analogues result from reactions of the type:407
R,P(O)X
+ (Me,Si),E
-+ Me,SiX
+ R,P(E)OSiMe,
(7)
R = X = ForCF,,E = O o r S
Complete spectroscopic data are presented to confirm the structures. Esters

containing P-S-Si
units are thermally much less stable than the oxygen
analogues, and with hydrogen chloride F,P(S)SSiMe, is converted into the
acid F,P(S)SH. Reactions with dimethylamine to give derivatives of the
anion F(Me,N)POO- and the thio-analogues are also described. The reactions
shown in equation (7) are considered to proceed via a five-co-ordinate intermediate R2P(OSiM~),X,which has been isolated for R = X = CF3.408
From n.m.r. data, the compound is fluxional with a structure based on two
axial and one equatorial CF, group.
On fluorination with either ammonium fluoride or KHF, the ylides
Me,P: CH2 and Et,P :CHCH, give, respectively, tetramethyl- and tetraethylfluorophosphorane,~sand although the former behaves as an ionic solid,
the latter is a molecular five-co-ordinate species. Addition compounds
formulated as the phosphonium derivatives M e , P S b M e 4 Fand
~ MePBuz
SbMe,F; result from reactions between Me4SbF and either Me,PF or
MeBu,PF.
Compounds containing P-0 Bonds. Electron-diffraction data410for bis(difluorophosphino)ether, F2POPFz, have been interpreted in terms of a C ,
structure with LPOP = 145 O , P-F = 1.597(4), and P-0 = 1.533(6) A.
Equilibration between (CF,),POP(CF,), and F2POPFz and the mixed
compound (CF3),POPF2 occurred within three days at room temperature.4ll
Equilibrium constants are much greater than the statistical value and are
probably associated with stability conferred on the mixed compound by the
greater 7r-acceptor properties of the (CF,),P group. Equilibrium also favoured
(CF,),PSPF, in the corresponding sulphur system but no reaction occurred
with the -NMebridged species below 150 "C, and above this temperature
the tetrafluoride decomposed.
406
*07
408
409
410
411
C. G. Moreland, G. 0. Doak, and L. B. Littlefield,J. Amer. Chem. SOC.,1973,95,255.

R. G. Cavell, R. D. Leary, and A. J. Tomlinson, Inorg. Chem., 1972,11,2573.
R. G. Cavell R. D. Leary, and A. J. Tomlinson, Inorg. Chem., 1972,11,2578.
H . Schmidbaur, K.-H. Mitschke, W. Buchner, H. Stuhler, and J. Weidlein, Chem.
Ber., 1973, 106, 1226.
D. E. J. Arnold and D. W. H . Rankin, J. Fluorine Chem., 1973, 2, 405.
R. G. Cavell and A. R. Sanger, Inorg. Nuclear Chem. Letters, 1973,9,461.
490
The perfluorocarboxylicacid esters of difluorophosphine, RfC(0)OPF,,412

undergo nucleophilic cleavage with halide ion to give acyl halides R,C(O)X,
and similar products result when the latter is replaced by a phosphorus(v)
species such as POF2X. With P203F4,however, the product is the carboxylic
anhydride RfC(0)OPOF2.
Full chemical-shift and coupling-constant data for OPF2H, SPF,H, and
SePF,H have been obtained from l H and 19Fn.m.r. measurements using
heteronuclear spin-decoupling techniq~es.4~~
The synthesis of POF, and P203F4from phosphorus pentafluoride, oxygen,
and magnesium at 300 "C has been described.414 There is an instantaneous
reaction between phosphoryl fluoride and nitrosyl fluoride at room temperature to give PF; as the only fluorine species p r e ~ e n t . 4Reaction
~~
with the
Group I fluorides is similar but slower and is represented by the equation:
3MF
+ 3POFs
2MPF8
+ MPOs
There is no evidence for the formation of either POF; or P02F;, as claimed

in earlier work. Tris(trimethylsily1)amine and phosphoryl fluoride react
to give an N-(difluorophosphory1)silylamine 0PF,N(SiMe3),,4l6 which can be
converted by treatment with P203F4into the bis(difluorophosphory1) derivative (OPF2),N(SiMe3). The reaction with phosphoryl chloride, on the other
hand, gives Me3SiOPC12:NSiMe,.
Trifluoromethyl hydroperoxide, CF,OOH, reacts with P203F4to give the
new compound CF300POF,, while with F,POPOF, the product is
CF30POF2.417Both compounds were characterized by i.r. and n.m.r. measurements and a number of reactions of the peroxy-compound are described.
Hydrolysis studiesg1* on 00-diethyl phosphorofluoridate (EtO),POF give
the equilibrium constant as 8.3 x lo5,the large difference from the value for
fluorophosphoric acid (ca. 43) being attributed to solvation effects.
Two fluoro-oxy-diphosphate(1v) species, Na3(P205F),12H,O and
K2(P204F2),have been isolated from the oxidation of red phosphorus in the
presence of fluoride ion?1g Detailed 19Fand 31P n.m.r. data are given.42o(See
ref. 266 for analogous amido-compounds).
Space-group and unit-cell data are given for a number of fluorophosphates,
e.g. M2P03F (M = NH,, K, or Rb)421and LiMP03F (M = Na, K, NH,,
Rb, Cs, or N2H5).422Data for two forms of anhydrous Na2P03F and two
412
G. E. Graves and M. Lustig, J. Fluorine Chem., 1973, 2, 321.
413
D.W. W. Anderson, E. A. V. Ebsworth, G. D. Meikle, and D. W. H. Rankin, Mol.
Phys., 1973,25, 381.

A. P. Hagen and E. A. Elphingstone, Synth. Inorg. Metal-org. Chem., 1972,2,335.
415 H. Selig and N. Aminadav, J . Znorg. Nuclear Chem., 1973, 35, 3371.
416 G.Czieslik, G. Flaskerud, R. Hofer, and 0. Glemser, Chem., Ber., 1973, 106, 399.
417 G.E. Graves and D. D. Desmarteau, J. Fluorine Chem., 1973, 2, 315.
418 H.C.Froede and I. B. Wilson, J. Amer. Chem. Soc., 1973,95,1987.
419 H. Falius, 2. anorg. Chem., 1972,394, 217.
4 2 0 H.Falius and M. Murray, J. Magn. Resonance, 1973, 10, 127.
421 J. Durand, W. Granier, G. Vilminot, and L. Cot, Compt. rend., 1972, 275, C, 737.
42a J. Durand, W. Granier, L. Cot, and C. Avinens, Compt. rend., 1973,277, C, 13.
414
Elements of Group V
491
types of double salts, e.g. NaK,(PO,F), hexagonal and NaNH4(P03F)
orthorhombic, which depend on cation size, have been obtained.423
A number of new fluorophosphate oligomers considered to belong to the
series (51) can be isolated by fractional precipitation from an aqueous solu-
(51) n = 1-3
tion of a fluorophosphate
Compounds with the stoicheiometry
Ba,(P,01,F,),6H20, Ba2K(P50,4F,),5H,0, and Ba,(P,0,F,)2 have been
obtained.
Vibrational data for the mixed phosphoryl and thiophosphoryl halides have
been analysed to give force constants425and thermodynamic
Electron-diffraction data427show that the most probable conformation
for trimethylene chlorophosphite (52) is a chair with the chlorine atom in an
742-0,
CH
P-Cl
%I2-,/
(52)
axial position; previous evidence had indicated an equatorial position for the
chlorine.
Analysis of the rotational spectrum of POCl, in the 18.0-40.0 GHz region
gives thefoll~wingparameters:~~~r(P=O)
1.455(5) A, r(P-Cl) 1.989(2)A, and
LClPCl 103.7(2)', and new values for the isothermal compressibility, specific
heat, etc., have been obtained429from measurements of the velocity of sound
in liquid phosphoryl chloride.
White solids previously reported in the pyridinePOC1, system are probably mixtures of pyridine hydrochloride and py,HOPOCl, that are due to the
presence of m o i ~ t u r e , and
4 ~ ~a re-examination of the system shows the presence
of a simple eutectic at 76.4%pyridine and -55.6OC. With Pel,, the compound 2py,PCI, (m.p. -42 "C)is formed, which gives a crystalline precipitate
2py,PC13,H,0 on treatment with moisture. Chloroformamidines (53) result
423
424
435
426
427
428
4aD
430
J. Durand, W. Granier, and L. Cot, Compt. rend., 1973,277, C, 101.

H. Grunze, J. Weels, and I. Grunze, 2. anorg. Chem., 1973, 400, 137.
A. Muller, F. Koniger, S. J. Cyvin, and A. Fadini, Spectrochim. Acta, 1973,29A, 219.
G. Nagarajan, Z . phys. Chem. (Leipzig), 1972,251,217.
V. A. Naumov and N. M. Zaripov, J. Struct. Chem., 1972, 13, 722.
Y. S . Li, M. M. Chen, and J. R. Durig, J . Mol. Structure, 1972,14,261.
M. V. Kaulgud and K. S. M. Rao, 2.phys. Chem. (Frankfurt), 1973,85, 326.
R. G. Makitra, M. S . Makaruk, and M. N. Didych, J. Chem. Gen. (U.S.S.R.), 1972,
42, 1872.
492
when dialkyl cyanamides react431with either phosphoryl or thiophosphoryl

chlorides:
RzN-CJN
XPC&
X =OorS
R2N-C=N-PC12
I
c1
xI
(53)
Reactions between phosphoryl chloride and both uni- and multi-dentate

phosphines have been investigated.432With triethylphosphine the product is a
dichlorophosphorylphosphonium salt (54), but with bis(diphenylphosphin0)ethane, compound (55) results. Hydrolysis gives the corresponding phosphine
[Et3P-PC12]Cl
II
0
(54)
[C12P-PPh2-CH2-CHrPPh~PCl]Clz
II
It
0
(55)
oxides. Analogous reactions with PSCl, give no salt-like intermediates, and

phosphine sulphides are formed immediately.
Thermal analysis of the TiBr4-POCl, system shows the existence of
2TiBr4,POCl,, TiBrp,POC1,, and TiBr4,2POCl,, with melting points of 84,
94, and 104 C, respectively,4= and the interaction of POC1, with TaCl, and
WCl, in the vapour phase gives a 1 :1 adduct in each case.434Formation of the
adducts NbCI,,POCI, and NbCl,,POBr, in chloroform solution has been
studied by 31Pn.m.r. spectros~opy:~5 giving values for the enthalpy and
entropy of activation for exchange of bulk and co-ordinated POCI, of 17 f
3 kcal mol-l and 18 f 10 cal deg-I mol-l, respectively.
Treatment of bismuth trichloride in POCl, solution with C1,O gives
Bi(P0,C1,),POCl,,436which has an i.r. spectrum consistent with co-ordination
of bismuth to the oxygen atom of the solvate POCI, molecule and to oxygen
of the PO,Cl, group, which behaves as a bidentate ligand. A monomeric
molybdenum compound, MoO,Cl,,POCI,, results from similar reactions
with MoC~,,~,but a polymer, Mo02(02PC12),POC1, (56), is obtained
431
43=
433
4S4
435
436
437
N. Schindler, Chem. Ber., 1973, 106, 56.

E. Lindner and H . Beer, Chem. Ber., 1972, 105, 3261.
A. V. Suvorov and D. Sharipov, Rum. J . Inorg. Chem., 1973, 18, 605.
A. M. German, A. V. Suvorov, V. A. Titov, and V. I. Trusov, Russ. J. Inorg. Chem.,
1972, 17, 1630.
J. C. Bunzli and A. Merbach, Helv. Chim. A d a , 1972,55,2867.
A. Klopsch and K. Dehnicke, 2. Naturforsch., 1972, 27b, 1304.
K. Dehnicke and A.-F. Sihada, 2. Naturforsch., 1973, 28b, 148.
Elements of Group V
493
when MoC1, reacts with P,o&l,. Silicon dichlorophosphates H [Si(P02Cl,),
and Si(PO,Cl,), can be obtained438by reactions with SiCl, or SiHCI,; the
properties and possible structures based on dichlorophosphate behaving as a
bidentate ligand are discussed.
Crystallographic results show that there are strong intermolecular intera c t i o n ~between
~ ~ ~ the oxygen atom and one of the halogens in both solid
POCl, and solid POBr,, but similar interactions in PSBr, are absent. These
results are compared with the extent of correlation splitting in the i.r. spectra.
The previously unknown phosphoryl iodide has been prepared440in 42%
yield by treating alkyl phosphoro-iodites ROPI, with iodine. Although the
phosphoro-iodites decompose slowly at -2OoC, they can be prepared by
reactions between the corresponding dichlorides and lithium iodide at low
temperatures.441Lower yields of POI,, which is obtained as dark violet
crystals melting at 50-53 "C, can be obtained from POCl, and lithium
iodide.4P0
Compounds containing P-S Bonds. The electronic structure of some thiocompounds Y,P=S, where Y = F, Cl, Br, OR, SR, or R, has been investigated by Wagner's formalism.442The PS bond character appears to be constant but the charges on the P or S atoms vary significantly. Difluorodithiophosphinic acid F2PS2Hforms c o m p l e x e ~with
~ ~ a*large
~ number of transition-metal chlorides [products shown in brackets], e.g. Cr0,C12 [Cr(S,PF,),],
MoOCl, [OMo(S2PF,),], MoCl, [Mo(S,PF,),], MoCl, [Mo(S,PF,),],
WOCl, [OWCl(S,PF,),], NbCl,, TaCl, [Cl,M(S,PF,),],
NbCl,, TiCl,
[Cl,M(S,PF,)], and VCl, [V(S,PF,),]. With vanadium, chromium, molybdenum, and tungsten compounds, products in a lower oxidation state are
obtained, and in general the reactivity of the halide decreases with reduction
of oxidation state. Vibrational and mass-spectrometricdata are presented for
all the compounds, in addition to magnetic measurements and details of the
electronic spectra.
1.r. and Raman spectra of compounds in the series OSPF;, S,PF;,
S,PFMe-, and S,P(CN); have been used to assess force constants using a
simplified valence force
Bonds to Nitrogen.-Phosphorus(rIr) Compounds. Resonance fluorescence has

been observedu6 for the diatomic molecule PN, produced in a microwave
discharge. Ab initio SCF-MO calculations for H,NPH2 indicate a trigonal
440
M. Meisel and H. Grunze, Z . anorg. Chem., 1973, 400, 128.

K. Ollie and D. J. Stufkens, Rec. Trav. chim., 1973, 92, 751.
V. G . Kostina, N. G. Feshchenko, and A. V. Kirsanov, J . Gen. Chem. (U.S.S.R.),
441
N. G. Feshchenko, V. G. Kostina, and A. V. Kirsanov, J . Gen. Chem. (U.S.S.R.),
442
P. Castan, A.-M. Alric, M.-C. Labarre, and R. Turpin, J. Chim. phys., 1973, 70,411.
R. G. Cavell and A. R. Sanger, Znorg. Chem., 1972, 11,2011.
R. G. Cavell and A. R. Sanger, Inorg. Chem., 1972, 11, 2016.
H . W. Roesky, R. Pantzer, and J. Goubeau, 2.anorg. Chem., 1972, 392, 42.
M. B. Moeller and S. J. Silvers, Chem. Phys. Letters, 1973, 19,78.
438
43s
1973, 43, 207.

1973,43,208.
443
444
445
44s
494
planar configuration at nitrogen owing to inductive release of electrons from

the PH,
Double-resonance techniques in conjunction with I5N
substitution have been usedu8 to determine the relative signs of the coupling
constants in H,SiNHPF,, disilylamine, trisilylamine, and H2NPF2.13Cn.m.r.
measurements for R1R2PNMe2compounds44Q
point to large positive values
for , J p ~ cwhen the CN bond is cis to the phosphorus lone pair but small,
negative values in the trans-conformation. l5N--lH coupling constants for
the labelled amino-phosphines F,PNH,, (CFS),PNH2, [(CF,),P],NH,
F,P(NH,),, F,PNH,, and some arsenic analogue~,4~~
can be rationalized on
the basis of redistribution of the 0-electrons, and it is unnecessary to invoke
N-P Irr-bonding.
The first compound (57) containing a double bond between a two-coordinate phosphorus(1n) atom and nitrogen has been obtained451by the
reaction :
(MesSi),NPF2
+ LiN(SiMeJ2
(Me3Si),NP:NSiMeS
+ LiF + Me,SiF
(57)
As expected, the compound is highly reactive and readily decomposes.

Phosphorus trifluoride reacts with NN-dimethylethylenediamine to give
(58),462 and a borine adduct is formed by attachment to the phosphorus
atom. In the 1 :1 boron trifluoride adduct, however, the donor site is nitrogen,
but 19Fn.m.r. spectroscopy shows the presence of two isomeric forms due to
different orientations of the P-F bond. Further BF, addition leads to reversible formation of (59). Reactions of cyclic and acyclic phosphoramidites
Me
&*-r2
\N-CHa
I
Me
with methyl iodide occur more slowly with the former, and the factors involved are discussed45sin terms of ring strain in the ground and transition
states.
Dimethoxychlorophosphine, (MeO),PCl, can be prepared in good yield
by displacing the dimethylamino-group in (MeO),PNMe2 with hydrogen
447
440
449
450
c51
452
46s
I. G. Csizmadia, A. H. Cowley, M. W. Taylor, C. M. Tel, and S. Wolfe, J.C.S. Chem.

Comm., 1972, 1147.
D. W. W. Anderson, J. E. Bentham, and D. W. H. Rankin, J.C.S. Dalton, 1973,1215.
M.-P. Simonnin, R.-M. Lequan, and F. W. Wehrli, J.C.S. Chem. Comm., 1972, 1204.
A. H. Cowley and J. R. Schweiger, J . Amer. Chem. SOC.,1973, 95, 4179.
E. Niecke and W. Flick, Angew. Chem. Internat. Edn., 1973,12,585.
S. Fleming, M. K. Lupton, and K. Jeket, Inorg. Chem., 1972,11,2534.
R. Greenhalgh and R. F. Hudson, Phosphorus, 1972,2, 1.
Elements of Group V
495
chloride, and the product reacts readily to give amine and N(SiMe,), derivat i v e ~ . *Alkylation
~~
of Me,NPC12 occurs with methylmagnesium bromide, and
anhydrous hydrogen cyanide displaces the amino-group in the product,
giving Me,PCN.455Redox reactions, e.g.
(Me,N),PCl 4- 2SbC15 ---+ [(Me2N)2PC1,]+[SbCI,](Me,N),POMe
+ SbCJ,
+ 2SbCI5 -+[(Me,N),P(OMe)Cl]+ [SbClJ- + SbCI,
occur when members of the series (Me2N),PC1,,45sa

and
(Me2N),P(OMe),,456b react with antimony pentachloride. A rn-carbaboranl-ylphosphonous acid, rn-HCIB,oHlaCP(0)H(OH), results when the product
from a reaction between (Et,N),PCl and rn-carbaboran-l-yl-lithiumis
treated with dry hydrogen chloride and then moist air;457the analogous
phosphonic acid has also been synthesized.
Up to four phenylimino-groups from phenyl azide can be added in a stepwise manner to the cage compound P,(NMe), according to recent 31P n.m.r.
mea~urernents,4~~
but only one group adds to the analogous P406molecule,
and no reaction occurred with either P4S3or P4. Stoicheiometric amounts of
sulphur can also be added to P4(NMe),, leading to the formation of three
new thiophosphorimides P4(NMe),S,, n = 1-3, which from spectroscopy
The
have structures analogous to those of P40,, P408, and P40g?59*460
tetraselenium analogue P4(NMeJ,Se4 can also be obtained.46o
Phosphorus(v) Compounds. The preparation and properties of compounds
containing the phosphazotrihalide, N=PX,, grouping have been
and physical and spectroscopic data for the compounds have been tabulated.462
N-Trimethylsilyltrichlorophosphinimine,Me,SiN :PCI,, which results
from treating phosphorus pentachloride with LiN(SiMe,),, is a hydrolysable
liquid which begins to split out Me,SiCl on heating to 100C.4s3Two reports464o46s
give the preparation of CICH,CCl,CCI,N :PCl, from phosphorus
pentachloride and acrylonitrile, but when the reaction is carried out in benzene at room temperature a hexachlorophosphate (60) is the
Acrylonitrile treated with a mixture of phosphorus tri- and penta-chlorides
at 60 "C gives a mixture of the cis- and trans-isomers (61) and (62),464which
454
456
456
457
0. J. Scherer and R. Thalacker, 2. Naturforsch., 1972, 27b, 1429.

E. A. Dietz, jun. and D. R. Martin, Inorg. Chem., 1973, 12, 241.
( a ) K. Press1 and A. Schmidt, Chem. Ber., 1972,105, 3518; (6) ibid., 1973,106,2217.
A. V. Kazantsev, M. N. Zhubekova, and L. I. Zakharkin, J. Gen. Chem. (U.S.S.R.),
1972.42, 1561.
458
459
460
461
463
463
464
465
M. Bermann and J. R. Van Wazer, Inorg. Chem., 1973, 12, 2186.

J. G. Riess and A. Wolff, J.C.S. Chem. Comm., 1972, 1050.
A. Wolff and J. G. Riess, Bull. SOC.chim. France, 1973, 1587.
M. Bermann, Adv. Inorg. Chem. Radiochem., 1972, 14, 1.
M. Bermam, Topics Phosphorus Chem., 1972,7, 311.
E. Niecke and W. Bitter, Inorg. Nuclear Chem. Letters, 1973, 9, 127.
E. Fluck and F. Horn, 2. anorg. Chem., 1973,398, 273.
H. A. Klein and H . P. Latscha, 2.anorg. Chem., 1973,399,225.
496

[ClCH2-C=C--N=PCla]
a$
PCI,
&I
(60)
c1
C1
c=c
/
ClCHn
,N=PCIa
c=c
\N=PCls
c*
ClCH2
/
can be partially hydrolysed with formic acid to the two -NHPOCl, isomers.
PCl, reactions with benzonitrile, terephthalodinitrile, and phthalodinitrile
in the presence of hydrogen chloride give respectively (63), (64), and (65)
as final products.466The benzonitrile reaction proceeds cia the intermediate
[P h - S N - P C l - N x -
I
c1
I
c1
Ph] PCIS
+
(63)
[PhC(Cl)=NPCl,]PCI, ; reactions with sulphur dioxide are described and
31Pn.m.r. data are given. (Other reactions with nitriles are described in refs.
565 and 566). With adipamide, H,NCO(CH,),CONH2, in a solvent, phosphorus pentachloride gives (C1,P=NCCl2CCl2CH2),, but in the absence of a
sdvent the dinitrile NC(CH,),CN is the product.467
On pyrolysis, compounds of the type R2PC1=NSO2X, where R = C1,
Me, or Ph and X = F or CI, give R,POCl and polymeric sulphanuric
derivatives [NS(0)X],,46s while analogous longer-chain species such as
E. Fluck and F. Horn, Phosphorus, 1973, 3, 59.
H. A. Klein and H. P. Latscha, 2. anorg. Chem., 1973, 396, 261.
W. Haubold, E. Fluck, and M. Becke-Goehring, 2.anorg. Chem., 1973, 397,269.
4 8 ~
487
468
Elements of Group V
497
Cl3P=NPCl2NS0,C1, on the other hand, give good yields of the P-N-S
heterocycles (66) and (67). Phosphorus-substituted aminoboranes
RiP(S)NR2BRi have been prepared469and the barrier to rotation about the
B-N bond is decreased by introduction of the R,P(S) group.

Diphenylthiophosphinylhydrazide, Ph,P(S)NHNH,, is obtained when the
corresponding chloride is treated with hydrazine hydrate,470and loss of hydrazine occurs on heating the compound to 80 'C,giving Ph2P(S)NHNHP(S)Ph2.
Pyrolysis of (MeO),P(O)N(SiM%)CH,SiMe,OEt gives, among other prodand
ucts, the heterocycle (68).471 Compounds of the type P(NR,),,&
OP(NR,),-,X,, where X = R, C1, OR, or F and x = 0-2, have been studied

by 31P and 19F n.m.r. and i.r. spectroscopy and magneto-optical measurem e n t ~to, ~show
~ ~ that the P-N bond has both CT and w character and that
the multiplicity of the P-N and P-0 bonds is related to effective electronegativity of the phosphorus atom. Chiral solvents affect the proton-decoupled 31Pn.m.r. spectrum of PP'-di(isopropy1)-NNN ' N '-tetramethylpyrophosphoramide through changes in the magnetic environment caused
by association of the optically active solvent with phosphoryl donor sites.473
Significantly different P-N bond lengths (1.604 and 1.628 A) in phenylphosphorodiamidate, PhOPO(NH,),, result from different hydrogen-bond
environments of the two nitrogen atoms according to a recent structure
determinati0n.4'~The distances imply more extensive P-N w-bonding than
469
470
471
478
475
474
H. Noth, D. Reiner, and W. Storch, Chem. Ber., 1973, 106, 1508.

H.-J. Jahns and L. Thielemann, Z . anorg. Chem., 1973, 3 9 7 , 4 7 .
V. S. Scheludyakov, E. S. Rodionov, A. I. Popov, and V. F. Mironov, J . Gen. Chem.
(U.S.S.R.), 1972, 42, 1643.
( a ) M.-C. Labarre and Y. Coustures, Compt. rend., 1973, 276, C, 133; (b) Y. COUStures, M.-C. Labarre, and M.-F. Bruniquel, Bull. SOC.chim. France, 1973, 926; (c)
M.-C. Labarre and Y. Coustures, J . Chim. phys., 1973, 70, 534.
M. D. Joesten, H . E. Smith, and V. A. Vix, jun., J.C.S. Chem. Comm., 1973,18.
G. J. Bullen and P. E. Dann, Acta Cryst., 1973, B29, 331.
498
in PO(NH&, and the P-0 distance (1.482 A) is also shorter than in the
triamide (1.510 A). The crystal structure of tris(octamethylmethy1enediphosphonic diamide) copper(I1) per~hlorate~'~
shows a slightly distorted octahedral
oxygen environment around copper, with the chelate molecules in a boat
~onformation.4~~
In endoxan, the cyclophosphamide (69), the ring is in the
chair form with the dialkylamino-group in an equatorial

this
is in contrast to observations on related systems where the amino-group
occupies an axial position.
Different stereochemical forms of the spiro phosphorus compounds (70)
obtained from ephedrine and norephedrine have been isolated.47s HCI
abstraction by sodium amide or sodium in liquid ammonia converts the

immonium salts (71) into the corresponding iminophosphoranes (72) ;479
further reactions leading to methylenephosphoranes are discussed.
(71) R' = Ra = MeaNorMe

R3 = H or Me
Accurate density, viscosity, and dielectric-const ant measurements for

hexamethylphosphortriamide are reported,480 and conductance measurements show that the solvent is a strongly differentiating medium for the donor
476
470
477
478
47s
480
P. T. Miller, P. G . Lmhert, and M. D. Joesten, Inorg. Chem., 1972, 11,2221.

J. C. Clardy, J. A. Mosbo, and J. G . Verkade, J.C.S. Chem. Comm., 1972, 1162.
S. Gracia-Bianco and A. Perales, Acta Cryst., 1972, B28, 2647.
R. Contreras, R. Wolf, and M. Sanchez, Synth. Inorg. Metal-org. Chem., 1973, 3 ,
37.
K. Issleib and M. Lischewski, Synth. Inorg. Metal-org. Chem., 1973,3, 155.
Yu. M. Kessler, M. G . Fomicheva, N. M. Alpatova, and V. P. Emelin, J . Sfrucf.
Chem., 1972,13,481.
Elements of Group V
499
strengths of halide and perchlorate ions.481Both lithium chloride and bromide
are completely dissociated in this solvent, but tetrabutylammonium salts are
associated. E.s.r. spectra of y-irradiated PO(NMe2), show an outer doublet
assigned to (Me,N),PO radicals and an inner triplet associated with
H,CNMePO(NMe,)
while i.r. and Raman spectra of the compound together with the changes taking place on dilution show that the
molecular symmetry is lower than C3v.483
Complex formation between PO(NMe,), and bromine has been followed
by lH n.m.r. spectro~copy,4~~
and the first five-co-ordinate complex of UIV
U(C104),,5[PO(NMe,),], has been isolated.485 A large number of new
nitrite-containing complexes of both hexamethylphosphortriamide (HMPA)
and nonamethylimidodiphosphoramide (NIPA) can be obtained!86 From
i.r. and visible spectra the nitrite groups are chelating in M(HMPA),(NO,),,
where M = Mg, Mn, Co, Ni, Cu, Zn, or Cd, and similar M(NIPA)(NO,),
compounds, but in Ni(NIPA),(NO,), both chelating and free nitrite groups
are present.
Mossbauer data for HMPA and NIPA complexes containing iron show
that in Fe(NIPA),X,, for example, the metal-ligand interaction is essentially
e l e ~ t r o v a l e n t .Metal
~ ~ ~ complexes of the potentially terdentate ligand (73)
NMe2
I
I II I II
Me o M e 0
(MQN)~P N-P-N--P(NMez)z
II
(73)
are
and from e.s.r. data in the bis-complexes ML,X2 the ligand
is considered to donate via the three oxygen atoms, giving a slightly distorted
octahedral arrangement around the metal. Trimorpholinophosphine oxide
gives complexes with the formula ML,(BF& with n = 0.54 for a wide
range of bivalent metals in which the metals are either tetrahedrally or octahedrally ~ o - o r d i n a t e d . ~ ~
Phosphoryl chloride reacts successively with aniline and ammonia to
produce PO(NHPh)(NH,),, which on heating loses ammonia with formation
of condensed amidophosphate~.~~~
A new phosphorus-nitrogen heterocycle
481
483
483
484
485
486
U. Mayer, V. Gutmann, and A. Lodzinska, Monatsh., 1973,104,1045.

K. V. S. Rao and M. C. R. Symons,J.C.S. Faraday II, 1972,68,2081.
M. T. Forel, Ann. Chim. (France), 1972,7,295.
Y . Ozari and J. Jagur-Grodzinski, J.C.S. Dalton, 1973,474.
J. G. H. du Preez and H. E. Rohwer, Inorg. Nuclear Chem. Letters, 1972, 8,921.
M.W. G. de Bolster, F. J. Wiegerink, and W. L. Groeneveld,J. Inorg. Nuclear Chem.,
1973, 35, 89.
48v M. W. G. de Bolster, A. Vermaas, and W. L. Groeneveld, J. Inorg. Nuclear Chem.,
1973,35, 83.
488
M. W. G. de Bolster, J. den Heijer, and W. L. Groeneveld, 2.Naturforsch., 1972,

27b, 1324.
M. W. G. de Bolster, I. E. Kortram, and W. L. Groeneveld,J. Inorg. Nuclear Chern.,
490
E. Kobayashi, Bull. Chem. Soc. Japan, 1973,46,183.
488
1973,35, 1843.
33
500
has been obtained from the reaction of formaldehyde and trimethylphosphoramide,491which from n.m.r. data, etc., is considered to have structure (74).
Me
Me
/Me
O=P-N-CH~-N-PP=O
N-CH2-N
Me
(75)
Me
(74)
Me
II
(MeNH)zfi-N-CH
N-P(NHMe)2
2-
Me
An intermediate (75) in this reaction can be isolated but there is also evidence
for species such as (76).
The reaction between NN'-bis(trimethylsily1)sulphur di-imide and phosphorus pentafluoride gives a small amount of S3N,PF,, for which (77) is the
suggested structure;492the 19Fn.m.r. spectrum shows two doublets,supporting
/i;"\pP-F
the presence of an equatorial and an axial fluorine atom. Phenyl groups in

Ph,P and Ph3P=NH are cleaved by the nucleophilic attack of NH; ions to
form salts of a nitrogen analogue of phenylphosphonic
e.g.
PbP
+ 2.5KNHz +
0.5NH3
PhP-NH
K2.6Ho.a
+ 4PhH
A series of anhydrous diamidophosphates POJNH,); of the Group I and

I1 metals have been prepared and their condensation reactions studied by
491
rez
4e3
H . L. Vandersall, D. L. Brooks, and C. W. Heitsch, Synth. Inorg. Metal-org. Chem.,

1973, 3, 267.
H. W. Roesky and 0. Petersen, Angew. Chem. Internat. Edn., 1973,12,415.
B. Ross and W. Dyroff, Z . anarg. Chem., 1973, 401, 57.
Elements of Group V
501
t .g.a.494The gel-chromatographic behaviour of cyclic and acyclic phosphoric
i r n i d o a m i d e ~and
~ ~ esters496
~
on Sephadex LH-20 has been investigated.
Pseudohalides. The reaction between either PF,Br or PF21 and sodium or
lithium azide to give PF2N,497is catalysed by traces of moisture, and the
compound reacts directly with diborane to give PF2N3,BH3.Both positiveand negative-ion mass spectra are reported for PF,X, where X = NCO,
NCS, or CN.498
The PFZ ion is the most abundant ion in the first, and although
doubly charged ions are of relatively high abundance, the PFZ+ ion is only
weak, suggesting that I(PFZ) is considerably higher than that of other singly
charged species; rearrangement ions are observed for each compound. The
X- ion is most abundant in the negative-ion spectra and the relative amount
of F- varies markedly with X.
00-Diphenyl phosphoryl azide, (PhO),PON,, can be obtained as a nonexplosive liquid from the corresponding choride and sodium azide in acetone,499*500
and the azido-group can be displaced by nucleophiles such as
water, butanol, ammonia, and a m i n e ~The
. ~ ~dialkyl
~
analogues501react with
trialkyl phosphites with elimination of nitrogen and the production of phosphinylphosphorimidic esters (R10),P=N-P(0)(OR2),.
Chlorination of (EtO),P(S)NCS gives EtOP(O)Cl(NCCl,), and in general
the chlorination of thiophosphoric esters yields substituted phosphoryl
halides.5021.r. and 31P n.m.r. data indicate that the cyanamide and dicyan-
methanide of triphenylphosphine are best represented as Ph,P=N=C=N

and Ph,P=C(C=N),, respectivelyF3
Compounds containing P-N-P

Bonds. Synthetic methods for the preparation
of compounds containing this unit have been reviewed.504Phosph(Iz1)azanes
result from reactions of phosphorus trichloride and three moles of a primary
a m i ~ ~with
e ; ~methyl
~
and ethyl amines the products have the formula
(C12P),NR but with the isopropyl and t-butyl compounds, cyclo-diphosphazanes (CIPNR), are the major products. The latter can be converted into
monoxides and monosulphides by reaction with, respectively, dimethyl
sulphoxide and sulphur. Cyclic dimeric and trimeric compounds are also
known for R = Et but these species have not been obtained pure. Other
494
K. KadiE, S. Skramovskg, and W. WanBk, Coll. Czech. Chem. Comm., 1972, 37,
3532.
4g8
M. Wolke, W. Topelmann, and H.-A. Lehmann, Z . anorg. Chem., 1973,396,212.

M. Wolke, W. Topelmann, and H.-A. Lehmann. 2. anorg. Chem., 1973,397, 157.
E. L. Lines and L. F. Centofanti, Inorg. Chem., 1972,11,2269.
D. W. H. Rankin, P. W. Harland, and J. C. J. Thynne, Inorg. Nuclear Chem. Letters,
499
T. Shiorini, K. Ninomiya, and S. Yamada, J , Amer. Chem. Soc., 1972,94,6203.
495
4g6
497
1972, 8, 1101.
500
501
502
503
504
506
R. J. W. Cremlyn, Austral. J. Chem., 1973, 26, 1591.

V. A. Gilyarov and M. I. Kabachnik, J . Gen. Chern. (U.S.S.R.), 1972,42, 2145.
W. Haubold and E. Fluck, 2. anorg. Chern., 1972,392, 59.
H. Kohler and B. Kotte, Z . Chem., 1973, 12, 350.
H. W. Roesky, Chem.-Ztg., 1972,96,487.
R. Jefferson, J. F. Nixon, T. M. Painter, R. Keat, and L. Stobbs,J.C.S. Dalton, 1973,
1414.

502
potential routes to the cyclic compounds have been explored, particularly
those involving heptamethyldisilazane, but products such as C12PNMeSiMe,
and (ClArP),NMe were obtained and not the cyclic phosphazanes. Both
mono- and di-sulphides can be prepared506by treating CI,PNRPC12 species
with elemental sulphur in the presence of aluminium chloride; the former lose
PC1, on heating to ca. 200 "C to give diphosphazanes [ClP(S)NRI2and the
latter give the same products, but temperatures of 25OoC are required to
eliminate PSCl,.
Crystal-structure determinations for (78) and (79) give the bond lengths
shown,507and in each case the distribution of bonds around the nitrogen atoms
is nearly planar. The P-N bonds are all short but differences in length can
be related to the formal positive charge on the phosphorus atom involved,
which increases in the order:
X
\..
,P-N
<
X
Chlorine-containing cations can be obtained by treating phosphinic thioamides with chlorophosphoranes according to the equations :508
RhP(S)NH2
RBP(S)NH,
+ RiPCb
-[
C
N
;C
P]-.'C
l-l
R1
R2
R1
R2
R;PSCl
R2PC14
R1 = R2 = M e o r P h
607
R. Keat, J.C.S. Dalton, 1972, 2189.

K. M. Ghouse, R. Keat, H. H. Mills, J. M. Robertson, T. S. Cameron, K. D.
Howlett, and C. K. Prout, Phosphorus, 1972, 2, 47.
A. Schmidpeter, N. Schindler, and H. Eiletz, Synth. Inorg. Metal-org. Chern., 1972,
2, 187.
Elements of Group V
503
The chlorine atoms in the cation react readily with ammonia while with
sulphur dioxide and formic acid the products are the neutral species
OPRiN=PR2C12 and HOPR1,=NPR2 (0)(OH), respectively. Full spectroC12P(Z)NMeP(S)F2
scopic data are reported for a series of new
and ClFP(Z)NMePSF,, where Z = 0 or S , prepared by treating PSF2Br
with P(Z)X2NHMe (X = F or C1) in the presence of triethylamine.
The same phosphazo-phosphonyl compound MeONP2C1, results from the
reaction of either phosphorus pentachloride and ethyl P-methyl phosphonamidate or methyltetrachlorophosphorane and diethyl phosphoramidate
(EtO),P(O)NH,, and although the structure could not be determined by
chemical means, formula (80) rather than the isomeric (81) is suggested by
35Cl n.q.r. measurements.5lO
X-Ray photoelectron spectrometric measurements511of the P(2p) and N(1s)

binding energies in the cation [Ph,P-N-PPh,]+
are interpreted to show
positive charge on the phosphorus atoms and negative character associated
with the nitrogen atom.
On alcoholysis, the diphosphazene ClzP(S)N=PCl,N=PCI,
gives an
S-alkyl derivative RSPC12=NPC12=NPOC12, presumably as a result of
migration.512Other polyphosphazenes can be prepared513by treating boron
trichloride and phosphorus pentachloride with ammonium chloride in 1,2dichloroethane. The products belong to the series [C1(C12P=N),PC13] [BCl,],
with the complexity depending primarily on the reaction temperature.
Compounds containing P2N2Rings. A number of diazadiphosphetidines (82),
(83), and (84) which are unsymmetrically substituted at either phosphorus or
nitrogen have been synthesized and examined by variable-temperature 19F
Me
/Y
MeF2p\N/PF2Ph
I
509
5L0
611
519
613
Me
Me
/N\
/N\
MeF*p\N/PFMe2
I
MeF2P\N/PF2Me
I
Me
Me
Ph
(82)
(83)
(84)
H. W. Roesky and W. Schaper, 2. Nuturforsch., 1972, 27b, 1137.

A. D. Gordeev, I. A. Kyuntsel, G. A. Golik, and V. A. Shokol, J . Gen. Chem.
(U.S.S.R.), 1973,43, 7.
W. E. Swartz, J. K. Ruff, and D. M. Hercules, J . Amer. Chem. SOC.,1972,94, 5227.
H. W. Roesky, 2. Naturforsch., 1972, 27b, 1569.
K. Niedenzu, I. A. Boenig, and E. B. Bradley, 2. unorg. Chem., 1972,393,88.
504
n.m.r. spectroscopy.514The results for (83) are significant in that it is possible

to differentiate between axial and equatorial fluorines below -40 "C,and
the results are consistent with a concerted pseudorotation at the two phosphorus atoms.
A crystal-structure determination515on the cyclodiphosphazene (85) (see
ref. 505 for the preparation) shows the presence of a planar P2N2ring with
the chlorine atoms in trans-positions. This is in contrast to the cis-arrangement of chlorine atoms in the phosphorus(rr1)precursor of (85). On pyrolysis,
PhPS(NHEt), yields two isomeric dithiocyclodiphosphazanes, and the
structure of the trans-isomer (86a) is reported.516Again the molecule contains
(86) a ; R = Et
b : R = Ph
a planar P,N, ring with distorted tetrahedral co-ordination around phosphorus

( L N P N = 83.3 O ) , and co-ordination around nitrogen is close to planar.
The structure517of the trans-N-Ph analogue (86b) is very similar, and the
molecule has overall symmetry close to C2h.
PhosphonitriZes (Phosphazenes). The island and delocalized models for the
r-bonding in these compounds have been reinvestigated to show that for
trimeric compounds the equivalent orbitals may be localized only by choosing
a particular non-variationally determined set of LCAO parameters.518 The
implications of this are considered further, but recent e.s.r. measurements519
seem to give direct experimentalevidence against extensiveelectron delocalization. Signals are observed which can only be assigned to an anion with an
unpaired electron localized on a single phosphorus atom and two chlorine
atoms. Dynamic nuclear polarization has been observed520in solutions of
(PNF,),, with a number of free radicals, including galvinoxyl and diphenylp icrylhydrazyl.
The previously unobserved symmetric PC12 deformation (v4) has been
located at 172 cm-l in a new Raman investigation on single crystals and
614
615
516
517
518
51B
580
0. Schlak, R. Schmutzler, R. K. Harris, and M. Murray, J.C.S. Chern. Comm., 1973,

23.
R. Keat, L. ManojloviGMuir, and K. W. Muir, Angew Chern. Internat. Edn., 1973,
12, 311.
G. J. Bullen, J. S. Rutherford, and P. A. Tucker, Acta Cryst., 1973, B29, 1439.
M. B. Peterson and A. J. Wagner, J.C.S. Dalton, 1973, 106.
G. Doggett, J.C.S. Faraday 11, 1972, 2075.
S. P. Mishra and M. C. R. Symons,J.C.S. Chern. Comm., 1973,313.
E. H. Poindexter, R. D. Bates, N. L. Paddock, and J. A. Potenza, J. Amer. Chern.
SOC.,1973,95, 1714.
Elements of Group V
505
solutions of P3N3C1,,521leading to a new assignment of the spectrum. Similar
crystal data have been obtained522on both the chloride and bromide, and
evidence is presented for slight non-planarity of the ring in solutions of
P&Br6. Force-constant calculations, using the Wilson FG matrix method,
have been carried out for the trimeric chloride and bromide but assignments
for the compounds cannot be unequivocally confirmed from the data presently available.523
New mixed halides with the formulae P3N3F,CI,-, and P3N3F,Br,,,
where n = 2-4,
when dimethylaminofluorotriphosphonitrilesare
treated with anhydrous hydrogen chloride or hydrogen bromide. An intermediate, P,N3F2Br3NMe2,consisting of three isomers, was isolated in the
reaction of P3N3F2(NMe2)4
with hydrogen bromide. All the compounds have
non-geminal structures and are produced as pairs of cis-trans-isomers. See,
for example, (87) and (88) for the structures of the P3N3F3X3isomers. The
isomers with n = 2 and 3 could be separated by g.l.c., and structures were

assigned unequivocally on the basis of 19Fn.m.r. data.
Evidence is presented for the presence of puckered P3N3rings in solutions
of cis- and trans-P3N3C1,(NMe2), from studies of the catalysed isomerizations
in acetonitrile and chloroform solutions.625Although the cis-isomer is the
more stable on the basis of enthalpy data, the trans has the higher entropy.
Kinetic measurements526show that replacement of the first two chlorine
atoms in P3N3CI, by dimethylamino-groupsin acetonitrile gives a cis-: transisomer ratio close to that found in the equilibration studies, and this implies
thermodynamic control. The isomer ratios for reactions in benzene, chloroform, and THF, on the other hand, indicate kinetic control of the course of
the reaction.
The P3N3 ring in cis-l,3,5-trichloro-l,3,5-tris(dimethylamino)triphosphonitrile has a slight chair conformation [P-N = 1.579(3) A, LPNP =
120.3(3)', and L N P N = 118.1(2)'] and the three phosphorus atoms are on
the same side of the mean ring plane as the chlorine atoms.527The P-Cl
5a1
623
533
ciZp
626
5p7
D. M. Adams and W. S. Fernando, J.C.S. Dalton, 1972, 2503.
J. A. Creighton and K. M. Thomas, Spectrochim. Acta, 1973,29A,1077.

K.S. Addison, T. R. Manley, and D. A. Williams, Spectrochim. Acta, 1973,29A,
821.
P. Clare, D. B. Sowerby, and B. Green, J.C.S. Dalton, 1972,2374.
J. M. E. Goldschmidt and M. Segev, Inorg. Nuclear Chem. Letters, 1973,9, 163.
J. M.E. Goldschmidt and M. Segev, Inorg. Nuclear Chem. Letters, 1973.9, 161.
F. R. Ahmed and D. R. Pollard, Acta Cryst., 1972,B28,3530.
506
distance is longer than that in P3N3CI, while the P-NMe, bond is shorter
than in a P(NMe,), group, indicating transfer of charge from the aminogroup to the chlorine on the same phosphorus atom. X-Ray photoelectron
spectrometry528for a series of chloro- and fluoro-dimethylaminotriphosphonitriles shows the expected reduction in the phosphorus 2p binding energy
as the chlorine atoms in P3N3CI, are replaced by electron-donating NMe,
groups; further, the binding energy of the ring nitrogen 1s electrons is lower
in P3N3(NMe,), than in P3N3C16.Results for mixed compounds are interpreted as indicating the ability of the ring system to redistribute charge, but
it seems clear that in P3N3(NMe,), the ring nitrogen atoms are more basic
than those of the amino-groups. Faraday-effect data529for compounds in the
series P3N3C16-,R,, R = NMe,, NHPr', or NHBd, show that there is a
straight-line relationship for compounds with strictly geminal structures.
Compounds with non-geminal structures have magneto-optic rotations above
the straight-line values, and it is suggested that magnetic exultation is in the
order trans > cis >gem.
An oxalyl derivative P3N3F5NHCOCONHF5P3N3
has been obtained when
P3N3F5NH2reacted with oxalyl chloride,530and tin-containing phosphonitriles, e.g. P3N3F5NMeSnMe3and P3N3F5N(SnMq),, from the treatment
of P3N3Fs with Me3SnNMeSnMe3.531Further treatment of the compounds
above with P,03F4 cleaves, in each case, a further Sn-N bond, and the
products are F2P(0)NMeP3N3F5and F,P(O)N(SnMe,)P,N,F,.
Attempts to
produce direct P-Sn bonds by replacing the chlorine atoms in P3N3C16
with Ph3SnLi or Bu;SnLi lead to breakdown of the ring system and isolation
O f Ph,Sn, Or BU6Sn2.632
The reaction of P,N,C16 with formamide in ether solution is known to
release hydrogen chloride and hydrogen cyanide, giving trimetaphosphimic
acid; the analogous reaction with t h i o f ~ r r n a m i d is
e ~slower
~ ~ but the addition
of pyridine speeds the process to give trimetathiophosphimic acid (89).
tias
630
631
632
633
B. Green, D. C. Ridley, and P. M. A. Sherwood,J.C.S. Dalton, 1973,1042.

M.F. Bruniquel, J.-P. Faucher, J.-F. Labarre, M. Hasan, S. S. Krishnamurthy, R. A.
Shaw, and M. Woods, Phosphorus, 1973,3,83.
H.Thamm, T. P. Lin, 0. Glemser, and E. Niecke, Z . Nuturforsch., 1972,27b,1431.
H.W.Roesky and H. Wiezer, Chem. Ber., 1973, 106,280.
H.Prakash and H. H. Sisler, Inorg. Chem., 1972,11,2258.
B. Yanik and V. Zheshutko, J. Geri. Chem. (U.S.S.R.),
1973,43,273,
Elements of Group V
507
Aluminium and indium chlorides react in aqueous solution with sodium trim e t a p h ~ s p h i m a t eto~ give
~ precipitates of M(P30,N3H3),5H,0, where M =
A1 or In, which dissolve on further addition of metaphosphimate owing to
complex formation. Species such as Na,Al(P,O,N,H,),, 10H,O can be isolated from concentrated solutions. The use of P3N3CI,, or mixtures with
higher hoinologues and linear material, at 100 "C as a dehydrating agent for
amides is described.535The products are nitriles, and a mechanism involving
the formation of diphosphoric and diphosphimic acids or their ammonium
salts is postulated.
Methods are given in Inorganic Syntheses536for the preparation of 1,lP,N,CI,(NH,), and P3N3C15NH2.The reaction of P3N3Br6with ammonia in
ether gives a diamino-c~mpound,~~~
which from 31P n.m.r. spectroscopy has
a geminal structure analogous to that of the corresponding chloride. A
similar structure is found for P3N3C14(NCS),,538which reacts with alcohols
and amines to give bis-thiourethane and thiourea derivatives, respectively.
Compounds in the series P,N,Cl,,(NHEt),
with n = 1 - 4 and 6 can be
prepared from the hexachloride and ethylamine in a suitable solvent,539and
in addition a hydrochloride of the hexasubstituted compound has been
isolated. When the mixed compounds are treated with dimethylamine the
chlorine atoms are completely replaced, and lH n.m.r. and basicity measurements on these compounds indicate that the initial stages of the ethylamine
reaction follow a non-geminal path. The tetrasubstituted compound is, however, the geminal (1,1,3,3-) derivative. Factors associated with both this
aspect and the increasing tendency toward geminal substitution with hindered
primary amines are considered.
The P3N3ring in P3N3(NMe2)6has a distorted boat conformation with all
P-N ring bonds equal in length [1.588(3) 81 according to single-crystal
X-ray results.540The overall molecular configuration is close to D, and the
mean exocyclic distance [I .652(4) A] indicates a contribution from rr-interaction. Treatment of the hexakis(dimethy1amine)-derivative with molybdenum trioxide in boiling water produces a crystalline ionic compound with
the formula 2 [P3N3(NMe2)6H]f[Mo6019]2-.Single-crystal X-ray analysis541
proves conclusivelythat protonation occurs at one of the ring nitrogen atoms
(the P-N ring bonds at this atom are 1.675 and 1.662 %, while others range
between 1.560 and 1.599 A). The hydrogen atom was located from a difference
Fourier analysis, giving N-H = 0.86(6) A.
Reactions of the geminally substituted compounds P3N3Ph2C14 and
534
535
536
537
538
538
540
541
I. A. Rozanov, V. R. Berdnikov, V. I. Sokol, and L. A. Butman, Izvest. Akad. Nauk.

S.S.S.R., Neorg. Materialy, 1973,9,152.
J. G. Graham and D. H. Marr, Canad. J. Chem., 1972,50, 3857.
G. R. Feistel, M. K. Feldt, R. L. Dieck, and T. Moeller, Inorg. Synth., 1973, 14, 23.
R. L. Dieck and T. Moeller, J. Inorg. Nuclear Chern., 1973, 35, 737.
R. L. Dieck and T. Moeller, J. Inorg. Nuclear Chem., 1973, 35, 75.
R. N. Das, R. A. Shaw, B. C. Smith, and M. Woods, J.C.S. Dalton, 1973, 709.
S. J. Rettig and J. Trotter, Canad. J. Chem., 1973, 51, 1295.
H. R. Allcock, E. C. Bisell, and E. T. Shaw, J . Amer. Chern. SOC.,1972, 94, 8603.

508
P3N3(NH2)2C14
with o-phenylenediamine give compounds
while the
major product from the reaction of P,N,CI,(OPh), with ammonia is the
(90)
diaminomon~chloride.~~
Benzophenone reacts with P3N,(OCH2CF3), to give
the fluoroethyl-substituted phosphoric acid (CF,CH,O),P(O)OH and 1,1,3triphenyl-1H - i ~ o i n d o l e . ~ ~
The previously unknown tetra- and penta-substituted compounds
P3N3C12(OBu), and P,N3CI (OBu), can be preparedu5 from the hexachloride
and respectively four or five moles of BunONa in THF at -78 ' C , and a
number of new fluoroalkoxy derivatives P3N3C1,(OCH,R),,,
where R =
C2F5or C3F,, x = 2 - 4 or 6, have been synthesized.546Reactions of P3N3Cl,
with the 2-, 3-, or 4-sodium methylot phenolates HOCH2C,H,0Na give diand tri-substituted compounds in addition to complete substit~tion,~'
and
on heating these products yield polymers with the liberation of water, hydrogen chloride, and formaldehyde.
Condensation reactions of the aminodiphosphazene (91) with substituted
phosphorus(1rr) halides give, instead of the expected cyclotriphosphazo-diene
RiP=N-PRi
NH2
II
NH
R2PXz
R2 = Me,Et,or OPh
(91) R1 = Me, Ph, or NMe2
RiP/NNpR;
ll
,hTH
N,
R2
(92)
Rip/N\PRi
II
"\"
'2R
\H
(93)
(92), a triphosphazo-triene (93).548 Spectroscopic methods indicate the presence of (93) only in the product, but the equilibrium with (92) is shown by the
642
G. F. Telegin, V. V. Kireev, and V. V. Korshak, J . Gen. Chem. (U.S.S.R.), 1972,

43, 1490.
643
644
545
H. Schadow and H. Scheler, 2. Chem., 1973,13,223.

R. A. Shaw and E. T. Mukmenev, Doklady Chem., 1973,208,48.
V. G. Sartaniya, V. V. Kireev, and V. V. Korshak, J . Gen. Chem. (U.S.S.R), 1973,
43, 677.
546
547
548
V. V. Korol'ko V. N. Sharov, V. N. Prons, and A. 0. Klebanskii, J. Gen. Chem.

(U.S.S.R.), 1973, 43, 586.
M. Kajiwara and H. Saito, Nippon Kagaku Kaishi, 1973, 500.
A. Schmidpeter, J. Ebeling, H. Stary, and C. Weingand, 2.anorg. Chem., 1972,394,
171.
Elements of Group V
509
ease with which methyl iodide reacts to give (94). The driving force for the
proton shift is considered to be the stabilization resulting from the formation
of the n-system in the cyclotriphosphazene. The spiro-compound (95) and
(94)
C
''
0
(95)
two other diazaphosphetidones (96) and (97) containing four-co-ordinate

phosphorus have been characteri~ed."~
The products of the reaction between P3N3C14(N=PCI,0H), and substituted sodium phenoxides are either amorphous solids or viscous liquids
with the formula P3N3(OAr)4[N=P(OAr),0H]2,550 and similar alkoxy-substituted compounds react with triphenylchlorosilane to replace one alkoxygroup in a side-chain by OSiPh,.551
The mixed methyl-fluoro-derivatives P4N4Fs_,Me,, where n = 1-4 or 8,
which result from reactions between P4N4F8and methyl-lithium in ether552
have been characterized by lH, 31P, and 19Fn.m.r. spectroscopy. Although
all five possible disubstituted compounds are obtained, the geminal isomer is
the most abundant, and in the tri- and tetra-substituted compounds the
geminal pattern is continued to give the antipodal (98) isomers. The reaction
Me
Me
4
/p=N\
\i'r
F N
\I
/N
"=p
M
'\e
F
(98)
549
560
551
55a
M. Bermann and J. R. Van Wazer, J.C.S. Dalton, 1973, 813.

A. A. Volodin, S. N. Zelenetskii, V. V. Kireev, and V. V. Korshak, J. Gen. Chem.
(U.S.S.R.), 1972, 43, 1497.
A. A. Volodin, V. V. Kireev, V. V. Korshak, E. A. Filippov, and V. M. Chukova,
J . Gen. Chem. (U.S.S.R.),1972, 43, 1493.
T. N. Ranganathan, S. M. Todd, and N. L. Paddock, Znorg. Chem., 1973,12,316.
510
hiorganic Chemistry of the Main-group Elements
(b)
Figure 9 The molecular structures of (a) cis,cis,trans, tran~-P,N,Cl,(NMe~)~

and (b) cis,cis,trans,trans-P,N,F,(NMe,),
(Reproduced from J.C.S. Dalton, 1972,2437 and 1973, 396, respectively)
between P4N4C18and dirneth~larnine,~~~

on the other hand, gives products
which depend not only on the quantity of amine added but also on the rate
at which it is added. With very slow rates, the maximum quantities of nongeminally substituted mixed compounds P,N,Cl,(NMe,),,
are obtained, but
increasing the rate gives both a greater spread of product stoicheiometries and
an increasing proportion of geminally substituted compounds. Isomers have
been separated for n = 3 (three compounds), n = 4 (four compounds), and
n = 5 (two compounds) and structures assigned on the basis of lH n.m.r.553
and i.r. spectroscopy.554
664
D. Millington and D. B. Sowerby, J.C.S. Dalton, 1972, 2035.

D. Millington and D. B. Sowerby, Spectrochim. Acta, 1973, 29A,765.
Elements of Group V
51 1
The hump which is often observed in the l H n.m.r. spectra of dimethylamino-phosphonitriles results from long-range virtual coupling and is
greatest where the substituted phosphorus atom in question is flanked by
equivalent phosphorus atoms.555This can thus serve as a useful guide to
structural assignment. X-Ray data show that in the non-geminally substituted
trans-isomers of both P4N,C16(NMe2)2556
and P4N4C12(NMe2),555
the ring has
a chair conformation, and in the PCl(NMe,) groups the amino-groupsoccupy
equatorial positions to minimize intramolecular contacts.
Single-crystal data have been reported for two non-geminally tetrasubstituted compounds P4N4C14(NMe)4557
and P4N4F4(NMe2),,558
in which the
substituents occupy cis-cis-trans-trans-orientations.
The ring bonds in each
case are similar in length but the ring conformations are substantially different.
The chloride adopts a hybrid crown-saddle conformation (see Figure 9a)
while the centrosymmetric fluoride has the chair conformation (see Figure
9b). In each case the ring angles at nitrogen vary, while a general feature is a
shortening of the P-N(amine) distance over that in P4N,(NMe2), and a
lengthening of the bonds to halogen over those found for the octafluoride
and octachloride.
In the complex [N6P6(NMe2)l,CoC1+]2[Co2C~~-],2CHC~,,
the metal in the
cation is bonded to a chlorine atom and four nitrogen atoms of the P,N,
ring in an arrangement best described as a distorted trigonal bipyramid
(see Figure
The symmetry of the ring is close to C2 and the overall
structure is similar to that of the copper complex?6oI.r., Raman, n.m.r., and
mass spectroscopic data are reported for the condensed tricyclic phosphonitrile P6N,Cl,.561 Attempts to replace the chlorine atoms with fluorine or methoxy-groups led to decomposition, but with dimethylamine both addition
and substitution occurred, and compound (99) was isolated.
G. J. Bullen, P. E. Dann, V. B. Desai, R. A. Shaw, B. C . Smith, and M. Woods,

Phosphorus, 1973,3,67.
6 5 6 G. J. Bullen and P. E. Dann, J.C.S. Dalton, 1973, 1453.
667 G. J. Bullen and P. A. Tucker, J.C.S. Dalton, 1972, 2437.
658 D. Millington, T. J. King, and D. B. Sowerby, J.C.S. Dalton, 1973, 396.
6 5 s W. Harrison and J. Trotter, J.C.S. Dalton, 1973, 61.
W. C. Marsh and J. Trotter, J. Chem. SOC.(A), 1971, 1482.
661 R. T. Oakley and N. L. Paddock, Canad. J . Chem., 1973,51,520.
655
512
Figure 10 The structure of [P,N,(NMe,),,CoC1+],[Co,CI~-],2CHCl3viewed

along b
The chlorine atoms in chloride high polymer, (PNCI,),, can be replaced

completely with RNH, (R = Me, Prn, Bun, or CF,CH,) but with more
bulky primary amines (R = Pri or Bui) or secondary amines the reaction is
incomplete.562Diethylamine, for example, substitutes half the chlorines nongeminally to give [PNCl(NEt,)],, which will react further with primary
amines, yielding mixed substituent polymers. The molecular weights calculated are ca. lo5, from ultracentrifugation and osmometry.
Heteroatom Ring Systems. Triazadiphosphorines (100) result from cyclocondensation reactions, in the presence of CCI,, of bis(diphenylphosphin0)amine and bifunctional amidines, guanines, isoureas, and i s o t h i ~ u r e a s , ~ ~ ~
and ionic compounds (RNHPPh2:NPPh,NH,)Cl are obtained when the

phosphino-amine reacts with ammonia, ButNH2, or PhNHNH, and carbon
662
H. R. Allcock, W.J. Cook, and D. P. Mack, Inorg. Chem., 1972, 11,2584.

and G . Saleh, Annalen, 1972,766, 98.
m3 R. Appel
Elements of Group V
513
tetrachloride. The values of P-P coupling constants in six-membered phosphonitriles can be related to parameters (AL) assigned to the groups attached
to the atoms involved.564Corresponding data for substituted triazadiphosphorines show that both Jpp and 1, values are lower than in the P3N3compounds, paralleling the smaller PNP angle in the former compounds.
Derivatives of the diazaphosphorine system (101) can be obtained by
treating 3-aminoa~rylonitriles~~~
or (aminomethylene)malononitriles566with
8
R-C /\C-Cl
/O\
Me2Si
II
SiMez
I
MeN
\p/NMe
N NP/ N
c1
Cl
PCI,. The former gives in addition the isomeric linear compound RlC(N=
PC13)=C(CN)R2, which is converted into the diazaphosphorine in the presence of HCl. Primary amine reactions with (101; R1 = Ph, R2 = CN) take
place rapidly, substituting one chlorine at the phosphorus atom first, then
replacing that at carbon before substituting the second chlorine at phosphorus.66*
A new heteroatom system (102) results from the reaction between RPCI,
(R = Me or Ph) and (MeNHSiMe,),O; the phosphorus atom is quaternized
by reaction with methyl iodide and with sulphur the thio-derivative is obtaix~ed.~~
Reactions of the mixed ring compound (103) with diphenylmercury
to give a monophenyl derivative and with AgF2 to give a difluoride are reported;568in each case i.r. spectroscopy showed that reaction took place at the
sulphur atom(s). Reactions of (103) with two moles of primary or secondary
amines, however, substituted one of the chlorines attached to phosphorus.569
Isomeric forms, (104) and (105), of a P,SN, system have been prepared according to the equations below, and the structures confirmed by 31P n.m.r.
[PhzP=N--PPh2]Cl
c1
+ SOZ(NHM~)~
c1
( 104)
K. Schumann and A. Schmidpeter, Phosphorus, 1973, 3, 57.

P. P. Kornuta, A. I. Kalenskaya, 0. P. Lobanov, and V. I. Shevchenko, J. Gen.
Chem. (U.S.S.R.), 1973, 43, 260.
m6 V. I. Shevchenko, A. I. Kalenskaya, and P. P. Kornuta, J . Gen. Chem. (U.S.S.R.),
1973,43, 13.
667 U. Wannagat, K.-P. Giesen, and H.-H. Falius, Monatsh., 1973, 104, 1444.
5 6 8 H. H. Baalmann and J. C . van de Grampel, Rec. Trav. chim., 1973,92,716.
U. Klingebiel, T. P. Lin, B. Buss, and 0. Glemser, Chern. Ber., 1973, 106,2969.
566
514
PClZ
CLP
II
II
N\ s / N
0//
Xo
measurements.570A tin-containing species (106) results from treatment of

S02(N=PC13), with (Me3Sn),N.531
Bonds to Oxygen.-Lower
Oxidation States. Configuration interaction
calculations have been carried out on the PO molecule using accurate SCFLCAO-MO wave function^.^^^ E.s.r. spectra show that t-butoxyl radicals add
to trialkyl p h o s p h i t e ~ to
~ ~produce
~ l ~ ~ ~phosphoranyl radicals BdOP(OR),,
and that phosphorus(1n) compounds and t-butylperoxyl radicals react by a
simple biniolecular reaction.574
The lH n.m.r. spectra of the oxy- and thio-compounds (107) can be analysed
in terms of an ABXYP spin system.575Reactions of both dioxo-phospholans
and dioxaphosphorinans with trimethylamine oxide give576the tetramethylammonium salts of the corresponding orthophosphoric acid, e.g. (108).
XMe
(107) X = 0 o r S
670
671
572
573
574
575
576
(108)
M. Bermann and J. R. Van Wazer, Inorg. Chem., 1972, 11, 2515.

A. L. Roche and H. Lefebvre-Brion, J. Chem. Phys., 1973,59, 1914.
P. J. Krusic, W. Mahler, and J. K. Kochi, J. Amer. Chem. SOC.,1972, 94, 6033.
G . B. Watts, D. Griller, and K. V. Ingold, J. Amer. Chem. SOC.,1972, 94, 8784.
E. Furimsky and J. A. Howard, J . Amer. Chem. SOC.,1973, 95, 369.
K. Bergesen and M. Bjoray, Acta Chem. Scnnd., 1973, 27, 357.
P. Chabrier and J.-F. Brault, Compt. rend., 1973, 276, C , 1135.
Elements of Group V
515
A white crystalline 1 :1 complex between copper hydride and tri-isopropyl
phosphite can be obtained in good yield,577showing the stabilizing influence
of phosphorus(II1) compounds on metal-hydrogen bonds via rr-bonding from
metal d-orbitals to phosphorus d-orbitals. The better r-acceptor (Me,N),P
forms 1 :1 and other complexes with CuCl, CuBr, and CuI. A phosphorus(rr1)
complex, Rh [P(OMe),]Q BPh;, is the first five-co-ordinatecomplex in which
stereochemical rigidity has been
but stereochemical non-rigidity
is found in some six-co-ordinate hydrides containing phosphorus l i g a n d ~ . ~ ' ~
Detailed information is given for the preparation of tetra-alkoxy-diphosp h i n e ~a, new
~ ~ ~class of compounds containing a P-P bond. For the higher
alkyl derivatives, the reaction is:
(RO),PH
EtsN
+ (R0)2PCl +
(RO)J'-P(OR),
but for lower alkyl compounds, which are stable only in solution, reduction
of (RO),PCl with a trialkyltin hydride is the method used. Reaction with
traces of oxygen gives pyrophosphites, but the P-P bond is retained in the
dithiohypophosphites obtained with sulphur.
1.r. and IH n.m.r. data for Sc(H,PO,),, Sc(HPO,),, Sc2(HP0,),,4H,0, and
Sc(H,PO,), indicate C,,symmetry for phosphite and C,,symmetry for hypophosphite,5a1 and crystallographic data are given for a number of bivalent
hypophosphites, M11(H,P02)2.582A new structure determination of the
magnesium salt Mg(H2P02),,6H,0 indicates P-0 and P-H distances in
the anion of 1.507 and 1.59 A, respectively,583and the magnesium is octahedrally co-ordinated by water molecules which are all involved in hydrogenbond formation with the hypophosphite anions.
Bridging hypophosphite groups are present in the structures of
La(H,PO,),,H,O and Eu(H,PO,),,H,O.~~~In Cu(H,PO,),, the copper is
surrounded by six oxygen atoms from different anions in a distorted octahedral arrangement, and the anions link together pairs of copper octahedra,
giving a co-ordination polymer structure.585
The radicals HPO;-, HP0;- and PO$- generated in aqueous solution from
Ti1I1and H,02with hypophosphorous and phosphorous acids all havepyramidal
677
578
579
580
581
582
584
585
34
M. A. Kazankova, I. G. Malykhina, M. B. Terenina, and I. F. Lutsenko, J. Gen.

Chem. (U.S.S.R.), 1972,42, 2129.
J. P. Jesson and P. Meakin, J . Amer. Chem. SOC.,1973,95,1345.
P. Meakin, E. L. Muetterties, and J. P. Jesson, J. Amer. Chem. SOC.,1973,95,75.
M. V. Proskurnina, A. L. Chekhun, and I. F. Lutsenko, J . Gen. Chem. (U.S.S.R.),
1973,43, 63.
L. N. Komissarova, E. G. Teterin, P. P. Mel'nikov, and V. F. Chuvaev, J. Struct.
Chem., 1972,13,784.
G . Brun, A. Norbert, and M. Caucanas-Dumail, Rev. Chim. midraze, 1972,9,581.
J. L. Galinge and Y . Dumas, Acta Cryst., 1973,B29, 1115.
V. M. Ionov, L. A. Aslanov, B. B. Rybakov, and M. A. Porai-Koshits, Soviet Phys.
Cryst., 1973, 18, 250, 252.
M. Handlovic, Chem. Zvesti, 1972,26, 494.
516
structures;586reactions with unsaturated compounds, etc., have been studied.
A mechanism involving a cation of the type HP0,H or HOPOsH has been

postulated from kinetic measurements on the Crv*oxidation of, respectively,
hypophosphorous and phosphorous
Semi-empirical LCAO-MO
calculations588of the energy-band structure of the infinite linear polyphosshow that 3d orbitals are greatly involved in the bondphite [-HP02--]
ing, and the results are generally consistent with the ready oxidation of such
species.
Solubility studies in the ZnHPO,-H,PO,-H,O
system have led to
the identification of Zn,H,(H3P30g),H,0, Zn,H,(H5P5015),1.5H20, and
ZnH2(H2P20,).589
Recent experiments show that in aqueous solution phosphite can be reduced to hypophosphite by U.V.
and reduction
of pyrophosphate and tripolyphosphate leads to species containing
phosphorus in lower oxidation states and chain lengths greater than
those of the reactants.591Electrophoretic analysis of an aqueous solution
of the products obtained by reactor irradiation of potassium phosphate shows
sharp peaks for only diphosphate, isohypophosphate, phosphate, phosphite,
and h y p o p h ~ s p h i t e , ~but
~ ~it" has recently been shown592bthat the chemical
form of the 32Pactivity in such experiments can be affected by treatment with
water. The use of liquid ammonia as solvent has therefore been suggested.
Phosphorus(v) Compounds. The chemistry of phosphate species containing a
peroxy linkage593and the stereochemical implications of reaction mechanisms
at phosphor us(^)^^^ have been reviewed. The cyclic 1,3,2-dioxaphospholans
derived from meso- and (&)-hydrobenzoin show different l H n.m.r. spectra,595and the crystal structures of the 2-~henoxy-~~,
and 2-p-bromophenoxy5-cliloromethyl-5-methyl-2-oxo-1,3,2-dioxaphosphorinans597
have been determined. Factors influencing the stereochemistry in substituted 1,3,2-dioxaphosphorinans as shown mainly by n.m.r. data are considered in a number
of paper^.^^**^ Changes in the 0-H stretching frequency of phenol in the
A. L. J. Beckwith, Austral. J. Chem., 1972, 25, 1887.
K. K. Sengupta, J. K. Chakladar, and A. K. Chatterjee, J. Inorg. Nuclear Chem.,
1973,35,901.
6 8 8 B. J. McAloon and P. G. Perkins, J.C.S. Faraday II, 1972, 1833.
689 M. Ebert and M. Pelikhnova, Coll. Czech. Chem. Comm., 1972,11,3672.
590 A. W. Schwartz and M. Van der Veen, Znorg. Nuclear Chem. Letters, 1973,9, 39.
sgl N. Yoza, M. Tokuda, T. Inoue, and S. Ohashi, Znorg. Nuclear Chem. Letters, 1973,
9,385.
(a) J. Fenger and P. B. Pagsberg, J. Inorg. Nuclear Chem., 1973, 35, 31 ; (b) A. G.
Maddock and A. J. Mahmood, Znorg. Nuclear Chem. Letters, 1973, 9, 509.
5 9 3 I. I. Creaser and J. 0. Edwards, Topics Phosphorus Chem., 1972,7, 379.
6n4 P. Gillespie, F. Ramirez, I. Ugi, and D. Marquarding, Angew. Chem. Internat. Edn.,
1973, 12, 91.
596 T. A. Modro and E. Skorupowa, Bull. Acad. polon. Sci., SJr. Sci. chim., 1972, 20,
399.
5 g 6 R. Wagner, W. Jensen, and W. Wadsworth, Cryst. Struct. Comm., 1973,2,507.
5s7 R. Wagner, W. Jensen, and W. Wadsworth, Cryst. Struct. Comm., 1973,2,327.
698 (a) W. G . Bentrude and H. W. Tan, J. Amer. Chem. SOC.,1972,94, 8223; (b) J. A.
Mosbo and J. G. Verkade, ibid., p. 8224; ( c ) ibid., 1973,95,204; ( d ) ibid., p. 4659.
586
687
Elements of Group V
517
presence of cyclic phosphates and phosphites give an indication of their
hydrogen-bonding tendencies, which correlates with the basicity of the phosphorus compounds; a similar correlation occurs with the Y ( ~ - frequency.599
~ )
The new six-co-ordinate phosphorus(v) species (log), isolated from a
reaction600between 1,3,2-benzodioxaphospholes,pyrocatechol, and triethyl-
amine, decomposes on heating to give the spirophosphorane (1 10). Kinetic

data show that hydrolysis of (PhO),P and its derivatives in a water-dimethoxyethane mixture is rapid and proceeds by way of a six-co-ordinate species.601
Full details of the structure of triethylammonium tris(u-pheny1enedioxy)pho.sphate, which also contains a six-co-ordinate phosphorus atom Ip-0 distances 1.723(4) and 1.706(4) A], have been published.602This distortion from
regularity and the slight non-planarity of the phenylenedioxyphosphole units
are ascribed to either hydrogen-bond formation or anion-cation interaction.
lH n.m.r. spectroscopy has been used to follow condensation in mixtures
of MePO(OMe), and Me,SiCl, to give oligomers with the formula
Me
I
ClfSiMe20-P-O~Me,603
and to assess the basicity of substituted phos-
II
phorus acids, MeP(O)XY, X = Y = PhO, H, OH, Ph, etc., in sulphuric

acid solution.s04
Crystal structures are reported for NH4[(Me0)2P021,605
Ag[(EtO)2P021,60s
and Mg [(EtO),P0,],,607 showing a distorted tetrahedral arrangement around
phosphorus with two long and two shorter P-0 distances. Co-ordination
about both Ag+ and Mg2+is tetrahedral.
A new peroxyphosphate, (EtO),P(O)OOCH(Me)Et, has been prepared from
diethyl phosphorochloridate and sodium s-butylperoxide.608
590
Goo
601
604
605
606
607
608
L. J. Van der Griend, D. W. White, and J. G. Verkade, Phosphorus, 1973,3,5.

M. Wieber and K. Foroughi, Angew. Chem. Internat. Edn., 1973, 12,419.
W. C. Archie, jun., and F. H. Westheimer, J . Amer. Chem. SOC.,1973,95,5955.
H. R. Allcock and E. C. Bisell, J . Amer. Chem. Soc., 1973, 95, 3154.
J. R. Van Wazer and S. H. Cook, Inorg. Chem., 1973,12,909.
A. G.Cook and G. W. Mason, J. Znorg. Nuclear Chem., 1973,35,2092.
L. Giarda, F. Garbassi, and M. Calcaterra, Acta Cryst., 1973, B29, 1826.
J. P. Hazel and R. L. Collin, Acta Cryst., 1972,B28, 2951.
F. S. Ezra and R. L. Collin, Acta Cryst., 1973,B29,1398.
V. V. Krysov, V. P. Maslennikov, and V. P. Sergeeva, J. Gen. Chem. ( U S S R . ) ,
1972,42, 1641.
518
Electron-diffraction measurements on trimethyl phosphate609 are best

interpreted by assuming the presence of two rotational isomers; the molecular
parameters reported are: d(P=O) 1.477; d(P-0) 1.580; d(0-C) 1.432A,
L O P 0 105.2', and LPOC 118.4'. Thermal condensation reactions610between
trialkyl phosphates and dialkyl phosphorochloridates give monophosphorus
side-products in addition to alkyl pyrophosphates. Detailed examinations of
such systems suggest that oxonium-type intermediates such as (111) are involved rather than quasi-phosphonium complexes.
(111)
The solvent properties of triethyl phosphate continue to be of interest.

Tin(1v) chloride dissolves to give mono- and di-solvates,611but with SnClg,2py
heterolysis of an Sn-Cl bond occurs and the reaction can be followed conductometrically. 1.r. and Raman data indicate that similar mono- and disolvates can be obtained from tributyl phosphate and both tin(Iv) chloride
and bromide.,12
Heteropolyacids. The structure of N~,Mo,P,O,,(H~~),~
contains anions in
which five MOO, octahedra form a ring by edge-sharing and two PO, tetrahedra are attached respectively above and below the ring;613each PO, unit
has one unshared oxygen atom. 1.r. spectra of molybdophosphoric acid
change on salt formation or when allowed to interact with ketones.g14Reduction of 12-molybdophosphoricacid by tin(1v) chloride proceeds through four
steps, in each of which the anion accepts two
giving phosphomolybdenum blue species with respectively 2 , 4 , 6 , and 8 of the molybdenum
atoms in the +5 oxidation state. Conditions have been established for the
formation of molybdo-titano-phosphate species616with the ratio 12:1 :1, and
a vanadomolybdophosphoric acid ~P,0,,8MoO3,2V,0,,nH,O has been
defined.,17
Four hydrated vanadotungstophosphoric acids, H3H[PWllVOgo],
H3H2 [pW~ov20401,H3H3 [pW9v30901, and H3Hg [pw~v~ogo1,
have been
H. Oberhammer, 2. Naturforsch., 1973, 28a, 1140.
A. Zwierzak, Phosphorus, 1972, 2, 19.
611 R. C. Paul, V. P. Kapila, and J. C . Bhatia, J. Inorg. Nuclear Chem., 1973,35, 833.
612 G . Roland, B. Gilbert, J. Decerf, and G. Duyckaerts, Spectrochim. A d a , 1973,29A,
879.
613 R. Strandberg, Acta Chem. Scand., 1973,27, 1004.
614 L. I. Lebedeva and M. N. Ptushkina, Russ. J. Znorg. Chem., 1972,17, 1118.
615 H. K. El-Shamy and M. Fiskander, J. Inorg. Nuclear Chem., 1973, 35, 1227.
616 L. P. Tsyganok, B. E. Reznik, V. D. Vorotyagina, and V. T. Chuiko, Rum. J . Inorg.
Chem., 1972, 17, 1115.
N. A. Polotebnova, Nguen Van Chen, and V. V. Kal'nibolotskaya, Russ. J. Inorg.
Chem., 1973, 18,216.
610
Elements of Group V
519
characterized by two g r o u p ~ , s ~ and
~ * ~the
l ~ new cobalt (11) derivatives
IPCo1*W~~O4oH2I5620 and [P2Co,(H,o)2W,8o68]"621 can be prepared.
Single-crystal data indicate that the latter consists of four edge-linked COO,
octahedra and two PW,,O;; structures.
Monophosphates. MO calculations using the two-atom differential-overlap
(TDOA) approach622imply substantial contribution to bonding from 3d
orbitals in POP, SO:-, and ClO;. The mean P-0 bond length in 62 phosphates is 1.537(9) A, and a regression analysis with cation electronegativity
shows a low
When the distance is corrected for mean oxygen
co-ordination the correlation is high, suggesting that the bond strength of the
non-tetrahedral cations affects the PO, distance; a similar argument is presented for the As-0 distance in arsenates.
A convenient preparation of crystalline phosphoric acid from the aqueous
acid and acetic anhydride has been described.624The acidity of phosphoric
in pure H t 8 0 has been found to be significantly less than in Hk60,
probably as a result of weaker hydrogen-bonding with H,180. Potentiometric
titrations confirm that in aqueous solutions dimers such as H,(PO,);,
H,(PO&-, and H,(PO,)> are formed in addition to the H,PO; and HP0;monomers.626Refinement of the crystal structure of one such dimeric species,
KH,(PO,),, by neutron diffraction627
showed the positions of all five hydrogen
atoms. The structure, shown in Figure 11, consists of two PO, tetrahedra
joined by a short hydrogen bond, with the four longer P-0 bonds also
carrying hydrogen atoms.
Phase transitions in KD2P04crystals have been i n v e ~ t i g a t e d ,and
~ ~ the
~.~~~
temperatures at which alkali-metal hydrogen phosphates are converted into
Phase
the diphosphate M4P207have been defined by d.t.a.
changes for the diphosphates are also given, and parallel studies on hydrogen
arsenates are described, New metastable phases containing vacancies have
been prepared for cobalt(r1) and magnesium or tho phosphate^.^^^
X-Ray powder diffraction and i.r. data are given for Mg(H2P04),,4H20
and for the dihydrate and anhydrous material obtained on heating;632further
N. A. Polotebnova, G. M. Shinik, and N. A. Dunaevskaya, Russ. J. Inorg. Chem.,
1973, 18,417.
619 D. P. Smith and M. T. Pope, Inorg. Chem., 1973,12,331.
620 T. J. R. Weakley, J.C.S. Dalton, 1973, 341.
621 T. J. R. Weakley, H. T. Evans, jun., J. S. Showell, G. F. TournC, and C. M. TournC,
J.C.S. Chem. Comm., 1973, 139.
6 2 2 S. P. Dolin and M. E. Dyatkina, J . Struct. Chem., 1972, 13, 838.
6 2 3 R. D. Shannon and C. Calvo, J. Solid-state Chem., 1973, 6 , 538.
6 2 4 D. C. Harper, Chem. andInd., 1973, 586.
c25 A. I. Kudish, D. Wolf, and S. Pinchas, J. Inorg. Nuclear Chem., 1973,35,3637.
6 2 6 A. A. Ivakin and E. M. Voronova, Russ. J . Inorg. Chem., 1973, 18, 465.
a27 E. Philipot, P. Richard, R. Roudault, and M. Maurin, Rev. Chim. minkrule, 1972,
9, 825.
628 E. V. Sidnenko and V. V. Gladkii, Soviet Phys. Cryst., 1973, 17, 861.
6 2 9 J.-J. Kim and D. T. Phillips, Nature Phys. Sci., 1973,242, 91.
630 K. Dostal, P. Fukanova, and L. Meznik, Coll. Czech. Chem. Comm., 1973,38,667.
631 G. Berthet, J. C. Joubert, and E. F. Bertraut, Z . Krist., 1972, 136, 98.
632 S. Ahmed, Pakistan J. Sci. Ind. Res., 1972, 15, 142.
618
520
heating to 397 OC gives Mg(PO,),.The dehydration of CaHP0,,2H20 over the

temperature range 409-537 K and a range of water-vapour partial pressures
appears to be controlled by the diffusion of water, and there is some evidence
for a monohydrate intermediate.633Mixed oxides of composition 0.1 <
P,O,/CaO < 0.6 have both acidic and basic properties, and as expected the
strength of the acid site becomes higher with increase in the P205/Ca0
Figure 11 The two PO, tetrahedra in KH,(PO,), joined by a short hydrogen

bond
(Reproduced by permission from Rev. Chim. miniraze, 1972,9, 825)
ratio?= The thermal dehydration of both Ba(H,P0,)235 and BaHP0,636

proceeds via a diphosphate, which for the former is converted into the tetrametaphosphate and linear polyphosphates above 270 OC.
Dehydration of an alumino-phosphate solution with a P205/A1203ratio
of 3.7: 1 gives initially crystalline A1(H2P04)3,which on further heating is
converted into a mixture of AI,H,,(P20,), and H2(AlP,01,),2H20.637The
final product obtained at 450-500 OC is the polyphosphate, free from oligophosphate impurities. The effect of phosphoric acid on thermal transformations of H3[A1(P0J2] has been studied.", l H n.m.r. spectra for Al(H2P04)3,
AIP0,,2H20, and a number of arsenic phosphates have been measured on
solid samples639and compared with calculated spectra. The PO4 tetrahedra
in Tl,PO, are slightly distorted, with each thallium atom co-ordinated to three
633
634
636
636
637
638
630
M. C. Ball and M. J. Casson, J.C.S. Dalton, 1973,34.
A. Tada and M. Yoshida, Chem. Letters, 1973, 311.

M.I. Kuz'menkov, V. V. Pechkovskii, and S. V. Plyshevskii, Russ. J. Inorg. Chem. ,
1972, 17, 985.
L. N. Shchegrov, Issled. Obl. Neorg. Tekknol., 1972,92.
M. I. Kuz'menkov, V. V. Pechkovskii, and I. T. Buraya, Russ. J . Inorg. Chem., 1973 ,
18,517.
A. N. Chivenkov, K. N. Lapko, A. K. Lobanok, A. N. Chivenko, and A. A. Soko1'chik, Vestsi Akad. Navuk Belarusk S.S.R., Ser. Khim. Navuk, 1973, 124.
C. Dorkmieux, M. Krahe, and F. d'Yvoire, Bull. SOC.chim. France, 1973, 409.
Elements of Group V
521
oxygen atoms of different phosphate groups according to recent X-ray inv e s t i g a t i o n ~205Tl
. ~ ~ ~n.m.r. studies of thallium phosphate glasses show that
the covalent character of the Tl-0 bond is greatest with T13P0, and decreases generally with decreasing thallium content.641
The compound Ge(OH)PO, consistsof chains with composition Ge(OH)O,,
which are connected by PO, tetrahedra into a three-dimensional network.642
From thermal analysis data the existence of NaPbO,, melting at 1117"C,
in the Na,PO,-Pb,(PO,),
system is confirmed, and in addition there is an
unidentified phase lying close to 10 mole% Pb3(P04)2.643
The solubility of
lead orthophosphate, PbHPO,, in dilute phosphoric acid solutions can be
interpreted in terms of the soluble species PbH,PO: and PbHP04.644Freeenergy of formation values for Pb,(P04),, PbS(P04)20H,and Pb,0(P0,)2
have been derived from hydrolysis data.
Interaction between bisrnuth(~ir)oxide and phosphoric acid leads to the
formation of the orthophosphate as the stable species up to 190C, but at
temperatures between 200 and 230 O C a tetrapolyphosphate is formed?45
Compounds obtained at higher temperatures from 4: 1 and 5 : 1 mixtures of
P205and Bi203may be ultraphosphates.
The transport of lanthanum and scandium orthophosphates by phosphorus pentachloride has been examined mass spe~trometrically,~~~
and
zircon-type structures have been confirmed by X-ray data for LuPO, and the
corresponding a r ~ e n a t e . ~Cerium(1v)
~'
phosphates648and phosphate sulp h a t e ~have
~ ~ been
~
synthesized and their ion-exchange properties investigated.
Wide-line lH and 31P n.m.r. measurements650led to a value of 1.87 A for
the H - - * P distance in Zr(HP04)2; values for all other H - - - H distances are
also given. The ion-exchange behaviour of crystalline zirconium phosphates
depends on the method of
and the details of the sodiumpotassium exchange on this material have been investigated by two
g r o ~ p s .The
~ ~ion-exchange
~ * ~ ~ ~ properties of chromium phosphates similarly
640
641
643
643
644
645
646
647
M. Ganne and M. Tournoux, Compt. rend., 1973,276, C, 1755.

L. Kolditz and E. Wahner, 2. anorg. Chem., 1973, 400, 161.
H. Mayer and 1. Vollenkle, 2. Krist., 1973, 136, 387.
R. K. Osterheld and J. D. Hawthorne, J . Solid-state Chem., 1973, 7 , 106.
J. 0. Nriagu, Inorg. Chem., 1972, 11,2499.
N. N. Chudinova, A. Lavrov, and I. V. Tananaev, Inorg. Materials, 1972, 8, 1733.
V. P. Orlovskii, E. A. Ionkina, and I. L. Agafonov, Inorg. Materials, 1972, 8, 1701.
G. Schmidt, B. Deppisch, V. Gramiich, and C. Scheringer, Acta Cryst., 1973, B29,
141.
64B
64Q
660
651
652
653
G. Alberti, U. Constantino, and L. Zsinka, J. Inorg. Nuclear Chem., 1972, 34, 3549.
K.-H. Konig and G. Eckstein, J . Inorg. Nuclear Chem., 1972,34,377; 1973,35,1359.
J. Fraissard, J. Chim. phys., 1973, 70, 101.
G. Alberti, U. Costantino, and M. Pelliccioni, J . Inorg. Nuclear Chem., 1973,35,1327;
G. Alberti, U. Costantino, S . Allulli, M. A. Massucci, and M. Pelliccioni, ibid., p.
1347.
G. Alberti, U. Costantino, S . A. Allulli, and M. A. Massucci, J . Inorg. Nuclear Chcm.,
1973,35, 1339.
A. Clearfield and A. S. Median, J . Inorg. Nuclear Chem., 1973,35,2985.
522
depend on the method of formation.654X-Ray powder data for CuTh2(P0,),

and TlTh,(PO,), are available.655
Differences in the behaviour of niobium and tantalum phosphates toward
bases are shown by an examination656
of the (M02),HP0,,2.5H20-KOH-H,O
systems (M = Nb or Ta). The final products are
and K14Nb1203,,27H20 and K,Ta60,,,16H,0, respectively. The crystalline mixed orthophosphates MMnP04,6H20,where M = Rb or Cs, can be dehydrated by
heating to 200-220 0C,657and two crystalline iron(u1) orthophosphates
which occur in Nature, i.e. strengite and phosphosiderite, have been synt h e s i ~ e dThere
. ~ ~ ~is evidence for a 1 :1 complex between osmium and phosphate ion from kinetic studies in aqueous systems.659The changes which occur
on heating CoHPO,, 1.5H2O and NiHP0,,2H20 have been
The only compound observed in a d.t.a. study of the AhP04-AgP03
system was the diphosphate Ag4P20,, which melts congruently at 643 oC.661
Equilibria in the Ag+-phosphoric acid system were examined by potentiometric titrations and give data for AgHPOy and AgH,P0,.662 Similar data
for Cd2+are described in terms of the formation of CdH,PO: and CdHP0,.663
The compounds ZnKP0,,664 Cd(H2P0,),,2H,0,665 and CdNaF0,,666 together with their arsenic analogues, have been prepared and X-ray powder
diffraction data obtained.
Apatites. Single-crystalX-ray data indicate that magnesium chlorophosphate,

Mg,(P04)Cl, is isostructural with the manganese c ~ m p o u n d . ~ ~ ~ Lamounts
arge
of calcium fluoride can be accommodated, probably in the channels, in the
structure of fluoroapatite, Ca,,(PO,),F,, with virtually no change in symmetry or unit-cell dimensions.668If the packing factor for fluorite is used, the
channels are effectively filled when the limit of solubility is reached. The
temperature for conversion of chloroapatite into chlorospodiosite, Ca,PO,Cl,
has been determined in a re-examination of the CaC12-Ca3(P04)2system.669
T. Akiyama and I. Tomita, J. Inorg. Nuclear Chem., 1973,35,2971.
M. Laugt, J. Appl. Cryst., 1973, 6, 299.
6 5 6 A. P. Shtin and E. I. Chernyavskaya, Russ. J. Inorg. Chem., 1972,17,1559.
657 B. V. Martynenko and M. V. Goloshchapov, Russ. J. Inorg. Chem., 1973, 18, 142.
6 5 8 L. S. Eshchenko, L. N. Shchegrov, V. V. Pechkovskii, and A. B. Ustimovich, Russ. J.
Inorg. Chem., 1973, 18,478.
6 5 9 G. A. Konishevskaya, V. F. Romanov, and K. B. Yatsimirskii, Russ. J. Inorg. Chem.,
1973, 18, 243.
6 6 0 V. V. Pechkovskii, L. N. Shchegrov, and E. D. Dzyuba, Issled. Obl. Neorg. Tekhnol.,
1972, 107.
661 R. K. Osterheld and T. J. Mozer, J . Inorg. Nuclear Chem., 1973,35,3463.
6 6 2 S. Hietanen, L.-G. Silltn, and E. Hogfeldt, Chemica Scripta, 1973,3,23.
6 6 s S. Hietanen, L.-G. Sillen, and E. Hogfeldt, Chemica Scripta, 1973,3, 65.
6 6 4 M. T. Averbuch-Pouchot and A. Durif, Materials Research Bull., 1973, 8, 353.
1313~M. T. Averbuch-Pouchot and A. Durif, Bull. SOC.f r a y . Minerale Crist., 1972,
95, 511.
6 6 6 M. T. Averbuch-Pouchot and A. Durif, Materials Research Bull., 1973,8,1.
667 J. R. Rea and E. Kostiner, Acta Cryst., 1972, B28, 3461.
6 6 8 A. W. Mann and A. G. Turner, Austral. J . Chem., 1972, 25, 2701.
66g J. Epperlein and H.-A. Lehmann, 2. Chem., 1973, 13,261.
654
665
Elements of Group V
523
X-Ray data show that the phosphate tetrahedra are less distorted in
Sr,(PO,),OH than in the isostructural h y d r o ~ y a p a t i t e . ~ ~ ~
Lead oxy-, hydroxy-, and alkali-metal apatites, Pb,o(P04)60,
Pblo(P0&(OH),, and Pb8M2(P0,)6, show differences in their i.r. spectra,671
and new lead phosphates with apatite-type structures but low Pb:P ratios
have been obtained.672X-Ray data for twin crystals of cadmium chloroapatite, Cd,(PO,),CI, point to the compound being isostructural with
f l ~ o r o a p a t i tand
e ~ ~the
~ problem of the twinning in these crystals is discussed
in relation to structural details.674
The B-type carbonato-apatites are derived from the hydroxy-apatite by
substitution of a phosphate ion by a carbonate i 0 n . 6 ~On
~ heating, the oxygen
in peroxy-apatites undergoes disproportionation to oxide ion and molecular
oxygen, and the extent to which the latter is retained varies with the dimensions of the channels in the
Apatites containing bivalent ions,
such as COi-, 02-,0;-,
and S2-, and those containing univalent ions in the
channels can be differentiated by i.r. spectroscopy.677Complex silicophosphates Sr4Ln6(SiO,),(PO4),,O,, where Ln = La, Nd, Y, or Er, have been
prepared and characterized678as members of a family of apatites with composit ion @+In6
(E4+04)4(E5+04)202.
Diphosphates. Improved values for the dissociation constants of diphosphoric

and tripolyphosphoric acids have been cal~ulated.8~~
The effect of the pressure
of water vapour on the reaction:
+ 2(NaPO,), + nH20
nNa2H2P,07
shows inhibition at high pressures,68oand on thermolysis there is a certain

temperature range where the reaction shows auto-inhibition.681
In the hemihydrate of potassium dihydrogen diphosphate, the anion is in
an approximately eclipsed cis-configuration with two unequal P-0 (bridge)
distances (1.57 and 1.63 A) and a POP angle of 13 1 o.682 The anions are linked
by a hydrogen-bond system to form a continuous
O-P-0-P-OH
* * *
O-P-0-P-OH
K. Sudarsanan and R. A. Young, Acta Cryst., 1972, B28, 3668.

G.Engel, J . Solid-State Chem., 1973, 6, 286.
G 7 2 G.Engel, J . Solid-state Chem., 1973,6,293.
673 K.Sudarsanan, R. A. Young, and J. D. H. Donnay, Acta Crysr., 1973, B29, 808.
6 7 4 K. Sudarsanan, R. A. Young, and J. D. H. Donnay, Acta Cryst., 1973, B29, 814.
6 7 5 J.-C. Labarthe, M. Therasse, G. Bouel, and G . Montel, Compt. rend., 1973,276, C ,
1175.
G 7 6 C Rey, J.-C. Trombe, and G. Montel, Compt. rend., 1973, 276, C, 1385.
~ 3 7 7 J.-C. Trombe and G. Montel, Compt. rend., 1973, 276, C, 1271.
6 7 8 N. F. Fedorov, I. F. Andreev, and Sh. Yu. Azimov, Russ. J . Inorg. Chem., 1972,17,
1537.
6 7 9 0. W. Edward, T. D. Fan, R. L. Dunn, and J. D. Hatfield, J . Chem. andEng. Data,
1973, 18, 24.
6 8 0 A. de Sallier Dupin and P. Dugleux, Compt. rend., 1972,275,C, 1211.
681 A. de Sallier Dupin and P. Dugleux, Compt. rend., 1972,275,C, 1463.
6 8 2 D.S. Emmerson and D. E. C. Corbridge, Phosphorus, 1972,2, 159.
670
671
524
spiral parallel to the b-axis. With Na,HP207,9H20, on the other hand, the
anion has a staggered trans-c~nfiguration,~~~
with bridge bond lengths and
angle of 1.62 A and 129.8', respectively. There are three P-0 distances of
1.516 A associated with one of the phosphorus atoms, while at the second
there are two of 1.493 and one of 1.585 A. The importance of hydrogen-bond
formation in determining the final structure is shown in these two studies and
in that on the structure of K,HP207,3H20.684Computer simulation techniques have been used, as the structure of cubic silicon diphosphate could not
be solved by conventional meth0ds.6~~
Incongruently melting compounds previously reported in the M,P,O,-MF
systems could not be substantiated, according to a reinvestigation.686Two
double salts, K2CdP,0,,4H20687 and Na,CdP20,,4H20,688 have been prepared and converted into the anhydrous materials; X-ray data are given for
the four species. Temperature-jump techniques have been used to study the
and three parallel
kinetics of diphosphate binding to magnesium i0ns,6~~
pathways involving P20F, HP,OF, and H,P20%-were postulated to interpret
the data.
Solvent-extraction studies of vanadium-(v) and -(Iv) in the presence of
diphosphate point to the involvement of species such as [V02(P207)2]7-and
[VO(P20,)]2-,
Hydrated manganese diphosphate, Mn2P20,,2H20, crystallizes in the
space group P2,/n. The bridge angle is 127.5(2)" and P-0 distances are
1.613(3)A, and the anion is 20 from the eclipsed ~onformation.6~~
In anhydrous cobalt diphosphate, the anion shows significant deviations from C,
symmetry as a result of six strong Co-0 bonds on one side and only five on
the other.6g2With one exception, all the terminal oxygen atoms are bonded
to two Co2+ions and one phosphorus atom. The unique oxygen, on the other
hand, is bonded to only one Co2+ and shows both the shortest P-0 and
Co-0 bonds in the structure. The bridge angle is 142.6' and the conformation is close to eclipsed.
Meta- and Poly-phosphates. The preparation, separation, structure, and

reactivity of cyclophosphates are the subjects treated in a recent review.69s
D. S. Emmerson and D. E. C. Corbridge, Phosphorus, 1973,3,75.
Y . Dumas, J. L. Galignb, and J. Falgueirettes, Acta Cryst., 1973, B29, 1623.
683 E. Tillmanns, W. Gebert, and W. H. Baur, J. Solid-state Chem., 1973, 7 , 69.
686 G. A. Bukholova, V. M. Shpakova, I. V. Mardirosova, and E. P. Babaeva, Russ. J.
Znorg. Chem., 1972, 17, 1479.
687 M. T. Averbuch-Pouchot, Bull. SOC.
frang. Minerale Crist., 1972, 95, 513.
6 8 8 G. A. Selivanova, N. T. Kudryavtsev, and Yu. M. Khozhainov, Russ. J. Znorg. Chem.,
1972,17, 806.
68D R. C . Patel and R. S. Taylor, J. Phys. Chem., 1973, 77,2318.
6Do I. A. Shevchuk, V. A. Sochneva, and Yu. V. Barabash, Russ. J. Inorg. Chem., 1973,
18, 529.
6D1 S. Schneider and R. L. Collin, Inorg. Chern., 1973, 12, 2136.
6D2 N. Krishnamachari and C. Calvo, Acta Cryst., 1972, B28,2883.
6D3 S. Y. Kalliney, Topics Phosphorus Chem., 1972,7,255.
683
684
Elements of Group V
525
In lithium trimetaphosphate trihydrate, the P309 ring has a chair conformation with ring angles of 130"and 101' at oxygen and phosphorus, respectively;
the lithium ions are tetrahedrally co-~rdinated.~~*
The thermal behaviour
and crystallographic constants for Li,P,O, ,3H,O, Li4P4OI2,6H20, and
(LiP03), have been described.695Sodium trimetaphosphate can be obtained
in high purity by heating mono-, di-, or tri-sodium phosphate at 100 "C with
an equi-volume mixture of acetic acid and acetic anhydride.6g6Pyrophosphate
and tripolyphosphate were observed as intermediates. The triphosphoric acid
derivative (1 12) results when sodium trimetaphosphate reacts with hexa0
II
I
II
11
I
HO-P-O-PP-O-P-NH(CH~)~NH~
ONa
ANa
ONa
(112)
methylenediamine,Bg7and the silver and barium salts can be prepared by

metathesis.
Evidence is presented698for ion-pair formation in solutions of cyclic phosphates, and species such as NaP40i; are found in tetrametaphosphate solutions and NaP,O:;,
Na2P60:;, and Na,P60i; for hexametaphosphate.
Further refinement6" of the original X-ray data for Na6(P60,,),6H,0 shows
that the ring has 2/m symmetry, with P-0 bridge and terminal distances of
1.613(4) and 1.471(4) A, respectively. These values are close to those in the
tetrametaphosphate.
Anhydrous trimetaphosphates MCaP,O,, where M = NayK, or NH,, can
be obtained by heating the hydrates, which crystallize from aqueous solution
to 180 "C.'O0 Further heating to 500 OC converts the sodium salt into a high
molecular weight polyphosphate while the potassium compound gives a
second trimetaphosphate modification. The ammonium salt loses ammonia
and phosphorus pentoxide to give calcium polyphosphate.
The effect of water content and heat treatment on the formation of aluminium phosphates, particularly A14(P40&, has been inve~tigated,~Ol*~O~
and
the changes in the properties of this material and AlPO, on grinding have
R. Masse, J. C. Grenier, G. Bassi, and I. Tordjman, Cryst. Struct. Comm., 1972, 1
239; 2.Krist., 1973, 137, 17.
6ss J. C. Grenier and A. Durif, Z . Krisf., 1973, 137, 10.
6 8 6 M. Watanabe and T. Senda, Bull. Chem. SOC.
Japan, 1972,45,2111.
6 9 7 N. M. Dombrovskii and A. I. Dorosh, Russ. J . Inorg. Chem., 1972,17,981.
6 s * G . Kura and S. Ohashi, J. Inorg. Nuclear Chem., 1972, 34, 3899.
6 Q s A. McAdam, K. H. Jost, and B. Beagley, Acra Cryst., 1972, B28, 2740.
'0 W. Feldmann, 2.anorg. Chem., 1973,400,97.
701 M. Tsuhako, K. Hasegawa, T. Matsuo, I. Motooka, and M. Kobayashi, Chem.
Letters, 1973, 367.
'Oa M. Tsuhako, K. Hasegawa, T. Matsuo, I. Motooka, and M. Kobayashi, Chem.
Letters, 1973, 573.
6s4
526
Inorganic Chemistry of the Main-gvoup Elements
been examined by X-ray methods, d.t.a., i.r. spectroscopy, etc.703(see also
refs. 637-639).
The rare-earth metaphosphates La(P,0,),4H20,704 Pr (P3O9),4H2O
,705a and
Er(P,0,),4.4H20705bcan be prepared, and the changes taking place on heating
have been investigated by X-ray, ix., and d.t.a. methods. In Cd,(P,O,),,14H,0,706eight of the water molecules are zeolitic and are located in large
channels formed by the arrangement of the P309 rings. Each cadmium is
octahedrally co-ordinated to four oxygens of two metaphosphate rings and
two water molecules. Equilibria in the nickel tetrametaphosphatesodium
metaphosphate system show the existence of the mixed sodium nickel trimetaph~sphate.~~~
A preliminary report708indicates that condensed phosphoric acids can be
obtained by treating aqueous phosphoric acid with cyanamide. Thermodynamic data have been obtained709for the interaction of a number of dipositive
cations in 1 :1 ratio with tripolyphosphate and HP,O;;.
The enthalpy terms
are relatively small but there is a correlation between the entropy of formation
and the ionic radius of the cation. A strong i.r. band at 1250-1300 cm-l
in the spectra of a large number of metal polyphosphates suggests that the
P=O bond character is not markedly changed by varying the cation.710The
insoluble Kurrol's salt KPO, can be converted into soluble K4P207 by
heating to 450 "C with KNO,, KNOz, or NaN0,.711
The metaphosphate Be(PO,),-I11 has the same crystal structure as the silicaK phase, with the silicon atoms being replaced by beryllium and phosphorus
in the ratio 1 :2.'12 This is the first example of a system having a silica-type
structure in which the atoms have been replaced in other than a 1 :1 ratio.
As part of an investigation of the CaO-Na,0-P20, system, the partial ternary
systems Ca(P0,),-Na20-P,05713 and Ca2P,0,-Ca(P03)2-Na,0714 were examined by thermal, microscopic, and X-ray analysis, and the corresponding
phase diagrams constructed. The structure of Ba,K(PO,),, the only compound
observed in the KP0,-Ba(PO,), system, contains a long PO, chain in the c
direction. The repeat period of ten tetrahedra is the longest observed thus far
in the polyphosphate field.716
703
704
705
706
707
708
70g
710
712
'13
'14
715
M. Tsuhako, I. Motooka, and M. Kobayashi, Bull. Chem. SOC.Japan, 1973, 46,

2343.
P. Birke and G. Kempe,Z. Chem., 1973, 13, 65.
( a ) P. Birke and G. Kempe, 2.Chem., 1973,13,110; (b) ibid., p. 151.
M. T. Averbuch-Pouchot, A. Durif, and I. Tordjman, Cryst. Struct. Comm., 1973,
2, 89.
E. L. Krivovyazov and L. L. Shutyi, Russ. J . Znorg. Chem., 1973, 18, 108.
R. Kitawaki, S. Oe, and I. Mogi, Nippon Kagaku Kaishi, 1972, 1546.
M. M. Taqui Khan and P. R. Reddy, J. Inorg. Nuclear Chem., 1973,35, 179.
R. C. Mehrotra, P. C. Vyas, and C. K. Oza, Indian J . Chem., 1972, 10, 726.
R. S. Hisar, Bull. SOC.chim. France, 1973, 2642.
E. Schultz and F. Liebau, Naturwiss., 1973, 60, 429.
J. Berak and T. Znamierowska, Roczniki Chem., 1972, 46, 1697.
J. Berak and T. Znamierowska, Roczniki Chem., 1972, 46, 1921.
C. Martin, I. Tordjman, and A. Mitschler, Crust. Struct. Comm., 1972, 1, 349.
Elements of Group V
527
Evidence for basic indium tripolyphosphates and the salt In5(P3010)3,21H20 comes from a study of the InC1,-Li,P,O,,-H,O
system.716 Thermal
transformations of this compound and the hydrated thallium717analogue
are reported. The structure of the compound Ge,O(PO,), consists of isolated
GeO, octahedra and Ge207double tetrahedra linked by PO, groups into a
three-dimensional network.718 Average distances are GeO, 1.863, GeO,
1.704, and PO4 1.525 A. Glass formation occurs in the NaPO,-Sb,O, system
with P: Sb ratios from 5 to 300.'19 The phosphate chain-length increases with
increase in the P: Sb ratio and is modified by the incorporation of three types
of Sb-0-P
linkages (1 13).
-p-o'-7Lo-p-
I
1
-P-
-O-Sb--O-P-
-P-
I
I
'0-Sb-0'
I
I
-PI
Heating a mixture of HaPo4 and V205 to 900 "C gives finally B-VP05,
which from single-crystal X-ray data contains chains of distorted octahedral
VO, groups linked together by phosphorus atoms;720the compound is isostructural with p-VS05. Methods of preparation and powder diffraction data
are given for both the a- and p-forms of VP05.721
The mixed triphosphates Na3M11P3010,12H20,where MI1 = Ni, Co,
Mn, Mg, Zn, or Cd, are isotypes and belong to the space group P2,/n (monoSingle-crystal data for Na,Cu(PO,), indicate the presence of infinite
(PO,) chains with a period of four PO, tetrahedra.723The barium compound
Ba,Cu(PO,), is observed in the Ba(PO,),-Cu(PO,), system,724but analogues
do not occur in the strontium or lead systems. Absorption spectra and bulk
properties are reported for glasses and melts in the Zn(PO,),-MPO, systems,
Crystallographic data have been obtained for
where M = Na, K, or
716
'17
710
720
721
722
733
724
736
G . V. Radicheva, E. N. Deichman, I. V. Tananaev, and V. V. Klimov, Russ. J.

Inorg. Chem., 1972, 17, 1199.
E. A. Prodan, M. M. Pavlyuchenko, L. I. Prodan, V. A. Sotnikova-Yuzhik, Yu. M.
Sotnikov-Yuzhik, and G . V. Peslyak, Znorg. Materials, 1972, 8 , 1329.
H. Mayer and H. Vollenkle, Monatsh, 1972, 103, 1560.
M. Watanabe, Bull. Chem. SOC.Japan, 1973, 46, 2468.
R. Gopal and C. Calvo, J . Solid State Chem., 1972,5,432.
E. Bordes, P. Courtine, and G . Pannetier, Ann. Chim. (France), 1973, 8 , 105.
E. Rakotomohanina, M.-T. Averbuch-Pouchot, and A. Durif, Bull. SOC.franc.
Minkrale Crist., 1972, 95, 516.
M. LBugt, I. Tordjman, J. C. Guitel, and G. Bassi, Cryst. Struct. Comm., 1972, 1,
279; Acta Cryst, 1972, B28, 2721.
M. Laugt, Compt. rend., 1972, 275, C, 1197.
E. L. Krivovyazov, B. F. Dzhurinskii, Kh. M. Rakhimbekova, and N. R. Voskesenskaya, Inorg. Materials, 1972, 8, 1445.
528

the high-temperature form of cadmium polyphosphate (/9726and the hydrated tripolyphosphates M,(P30,0)3,20H20 (M = Er or Yb).727
X-Ray data indicate that BiP,014 is an isotype of the ultraphosphate
LaP,O,,, and there are strong structural relations with the holmium comThe latter can be obtained in both orthorhombic (Pnrnu) and monoclinic (C2/c) forms, and the ultraphosphate structure for both is shown by
single-crystal r n e a s u r e m e n t ~ . ~ ~ ~ * ~ ~
Bonds to Sulphur or Selenium.-Structures (114) and (1 1 3 , respectively, are

assigned on the basis of i.r. data, etc., to the sulphides P4S9and P4S4obtained
s/p\s
/
\
P--
\dP
by slow cooling of a melt of P4S1, and red phosphorus.731A third compound,

P4S2 (116), can be prepared from P4S3and white phosphorus. 1.r. and Raman
studies point to the structure of P4S3remaining the same in the solid, melt,
and vapour phases.732The hepta- and deca-sulphides P4S7 and P4Slo suffer
little decomposition on melting, but loss of sulphur certainly occurs for both
in the gas phase. With P4S5,decomposition occurs even in the melt to give
P4S3,P4S7,and at least one further species.
The modes of reaction of the monothio-, monoseleno-, and selenothiophosphorus acids have been reviewed7%and the general properties of transit ion-metal dithio- and diseleno-phospha te complexes are given ,34 together
with data on ligand synthesis and spectroscopic properties. The dithiophosphinate ligand R,PS2 is placed before dithiophosphate in the spectrochemical
series from an examination of the visible spectra and magnetic properties of a
726
727
728
729
731
733
733
M. Lgugt, M. Bagieu-Beucher, and J.-C. Grenier, Compt. rend., 1972, 275, C , 1283.
S. M. Petushkova, V. G. Kuznetsov, I. V. Tananaev, and S. 0. Samoilova, Russ. J .
Inorg. Chem., 1972, 17, 1234.
N. N. Tschudinowa and K. H. Jost, Z . anorg. Chem., 1973,400,185.
D. Tranqui, M. Bagieu-Beucher and A. Durif, Bull. SOC.franc. Mitikale Crist.,
1972,95,437.
M. Bagieu, I. Tordjman, and G. Bassi, Cryst. Struct. Comm., 1973,2,387.
H. Vincent and C. Vincent-Forat, Bull. SOC.chim. France, 1973, 499.
M. Gardner, J.C.S. Dalton, 1973, 691.
J. Michalski and W. J. Stec, Chem.-Ztg., 1972, 96, 499.
J. R. Wasson, G. M. Woltermann, and H. J. Stoklosa, Fortschr. Chem. Forsch., 1973,
35, 65.
Elements of Group V
529
number of di@-t 01yl)dithiophosphinato-complexes.735 In catena-bis-p-(00'di-isopropy1dithiophosphate)-digold(r),the phosphate ligands bridge between
the two gold atoms, which are also linked by a metal-metal bond.736Organothallium(1m) dithiophosphates RT1 [S(S)P(OR),], can be prepared from
RTlC12 and the alkali-metal salts (RO),P(S)SM.737
Mild alkylation of (R,NCH,CH,O),P(S)SK gives the triesters, which are
unstable and undergo thione-thiol i s o m e r i ~ a t i o n Treatment
.~~~
of P2S5 with
alkanethiols in the presence of triethylamine produces the heterocycle (1 17),
which can be converted into the potassium salt by potassium e t h ~ x i d e , ' ~ ~
and a new heterocycle (118) results when P2T4and methanedithiol react in the
presence of p ~ r i d i n e . 'The
~ ~ lH n.m.r. spectrum of the diphosphine disulphide
(119) has been analysed in
and Jpp is determined as 118 f 5 Hz.
Although sodium azide completely cleaves the P2S2ring in alkyldithiophosphonic anhydrides, the heterocycle (120) can be obtained by using trimethylsilyl a ~ i d e . With
' ~ ~ the corresponding phenyldithiophosphonic anhydride, the
(119)
SiMe3
(120) R = M e o r E t
sulphanes (121) result on treatment with SCI, and S2C12,743

while with SOCI,
one obtains the oxygenated species (122).
735
736
737
738
739
740
741
743
743
R. N. Mukherjee, S. V. Shanbhag, R. P. Angadi, and H. N. Srivastava, Ifidian J.

Chem., 1973, 11,64.
S. L. Lawton, W. J. Rohrbaugh, and G . T. Kokotailo, Inorg. Chem., 1972, 11,2227.
B. Walther, 2.anorg. Chem., 1973,395, 112.
A. P. Gupalo and N. I. Zemlyanskii, J. Gen. Chem. (U.S.S.R.), 1972, 42, 1708.
N. I. Zemlyanskii, G. F. Belous, and I. V. Murav'ev,J. Gen. Chem. (U.S.S.R.), 1972,
42, 1639.
M. Baudler, K. Glinka, U. Kelsch, H. Sandmann, and W. Haller, Phosphorus, 1972,
2, 161.
G. Hagele, R. K. Harris, and J. M. Nichols, J.C.S. Dalton, 1973, 79.
H. W. Roesky and M. Dietl, Angew. Chem. Internat. Edn., 1973, 12,425.
E. Fluck, F. Ibaiiez, and H . Binder, Z . anorg. Chem., 1973,397,147.
530
S
Ph-P-(
II
I
Cl
S )n-P-Ph
c1
(121) n = 3 o r 4
(122)
The first member of the previously unknown class of phosphorus thiocyanates has been obtained by reaction between a sulphenyl chloride
(Me,CCH,O),P(O)SCl and silver cyanide at -5 0C.744
The compound has a
sharp i.r. band at 2170 cm-l but isomerizes after a few minutes at 25 OC to the
more stable isothiocyanate (broad band at 2010 cm-l).
Reactions are described in which the chlorine atom in the pyridinium
chlorodithiophosphate betaine (123) is replaced by fluoro-, bromo-, and
dimethylamino-groups; further reactions with alcohols give alkoxydithiophosphates, of which the fluorides (124) are particularly stable.745The
fluoro-betaine obtained as described above gives salts of the previously

unknown difluorotetrathiodiphosphoric acid (125) by reaction with acetic
acid, probably by way of the acetato-anion CH,COOPF(S)S-.746
Unusual long-range spin-spin coupling (7Jap= ca. 2.0 Hz) has been
observed in the l H n.m.r. spectra of tri-p-tolyl-tri- and-tetra-thioph~sphates,~~~
and similar results are found for the ortho-substituted isomers but not for the
meta. Structural data are reported for the trisubstituted 0 - , m-, and p-tolylphosphine s u l p h i d e ~ . ~ ~ ~
The Ph,PS radical is produced by X-irradiation of diphenylthiophos~ h i n eand
, ~ under
~ ~ y-irradiation trichlorosilane brings about the desulphuration of phosphine sulphides to phosphines and of phosphorothionates to
p h o ~ p h i t e sChloramine-T
.~~~
has been found to be a useful oxidant for distinguishing between a variety of structural units, particularly in phosphorussulphur compounds.751
744
A. Lopusinski and J. Michalski, Angew Chem. Internat. Edrt., 1972, 11, 838.
745
E. Fluck, P. J. Retuert, and H. Binder, Z . anorg. Chem., 1973,397,225.
746
E. Fluck and P. J. Retuert, Inorg. Nuclear Chem. Letters, 1973, 9, 305.
747
748
T.S. Cameron, K. D. Howlett, R. A. Shaw, and M.Woods, Phosphorus, 1973, 3,
749
750
751
R. A. Shaw and M. Woods, Phosphorus, 1972,2, 61.
71.
M. Geoffroy, Helv. Chim. Acta, 1973, 56, 1552.
R. Nakao, T. Fukumoto, and J. Tsurugi, Chem. Letters, 1973, 377.
D.K.Padman, R. A. Shaw, C. P. Thakur, A. R. V. Murthy, and M. Woods, Phosphorus, 1972,2,81.
Elements of Group V
53 1
A number of compounds with the stoicheiometry M,P2SB and M2P2Se6,

where M = Mg, Ca, Mn, Fe, Ni, Cd, Hg, Sn, or Pb, have been synthesized
by high-temperature reactions of stoicheiometric mixtures of the element~.~5~
X-Ray data for single crystals of the two iron compounds753show that both
form layer lattices, with double layers of the chalcogen atoms and the iron
atoms occupying octahedral sites. PZx6 units are present and the compounds
are characterized as hypodiphosphates.
Higher polysulphane-diphosphonates (03PS3P03)4- and (03PS4P03)4result from reactions between S 2 P 2 0 eand SP0;--,754while an alternative
preparative route involves interaction of the polysulphane disulphonates
with SP0k.755The latter method also yields polysulphane phosphonosulphonates (03P-Sn-S03)3-,
described here for the first time. Reactions of
SP0;- with seleno- and telluro-polythionates follow a similar course, and
among the products isolated75swere (O,PSSeSPO,)*-, (0,PSTeSP03)4-, and
(03PSSeSS0,)3-.
The trithiophosphate Na3(POS3),11H20and the arsenic analogue have been
substantiated and identified by X-ray diffra~tion,'~'and new assignments
have been given for the Raman spectrum of PS:- in
Rare-earth
orthothiophosphates LnPS,, where Ln = La, Ce, Pr, Nd, or Sm, result
when Ln2S3is fused with P,S,,,, at 700 OC; the products were characterized by
X-Ray data
X-ray diffraction and magnetic susceptibility
for crystals of GaPS, grown by vapour transport with iodine show that the
sulphur atoms are hexagonally close packed (slightly puckered layers), with
gallium and phosphorus atoms occupying tetrahedral holes in alternate
layers.760
Derivatives of P$e7 have been obtained by heating P4Se5 with heteroaromatic a r n i n e ~ and
, ~ ~among
~
the compounds isolated are P4Se7,3L,L =
pyridine or 4-methylpyridine, P4Se7,3L,and P4Se,,6L (L = 4-ethylpyridine).
The reaction with isoquinoline, on the other hand, gives a salt containing
the pyroselenophosphate anion (C,H7NH+)3(HP,Se7)3-. The 31P chemical
shift in glasses in the P-As-Se system is independent of the phosphorus concentration, and the materials under examination were not considered to
contain P-As bonds.7s2 Values of lJp-s, enable differentiation between
selenium in terminal and bridging positions, as the values for the latter are
the range for terminal atoms is from ca. 700 to 1100 Hz.
always
75a
7S3
754
7j5
758
757
7j8
7sB
'Go
763
7e3
35
W. Klingen, R. Ott, and H. Hahn, Z . anorg. Chem., 1973,396,271.

W. Klingen, G. Eulenberger, and H. Hahn, Z . anorg. Chem., 1973,401,97.
E. Blasius and N. Spannhake, Z . anorg. Chem., 1973,399,315.
E. Blasius and N. Spannhake, Z . anorg. Chem., 1973,399,321.
E. Blasius and N. Spannhake, Z . anorg. Chem., 1973, 399, 331.
M. Paiazzi, Bull. SOC.chim. France, 1973, 845.
A. Miiller, N. Mohan, P. Cristophliemk, I. Tossidis, and M. Drager, Spectrochim.
Acta, 1973,29A, 1345.
V. V. Yampol'skaya and V. V. Serebrennikov, Russ. J . Inorg. Chem., 1972, 17, 1771.
C. D. Mickey and R. A. Zingaro, Inorg. Chem., 1973,12,2115.
V. S. Tsarev and L. A. Baidakov, Inorg. Materials, 1972, 8, 1225.
W. J. Stec, A. Dkruszek, B. Uznanski, and J. Michalski, Phosphorus, 1972, 2, 97.

Red selenium reacts with PI, to give a good yield of PSeI, and with P,I,
in 2: 1 and 1 :1 mole ratios to give compounds (126) and (127), respectively.764
The presence of a P-P bond is indicated by 31P n.m.r. and i.r. spectra.
532
(126)
(127)
Single-crystal data indicate an enargite structure for Cu,PSe,, with Cu-Se

and P-Se bonds equal to 2.37 A and angles varying between 108.4 and
110.2.765
Cu,PS4 is an isotype, but the antimony analogues have the formatinite structure.
3 Arsenic
Element and Arsenides.-The
equilibrium :
has been
by the Knudsen cell-mass spectrometric technique over
solid MoAs, and Mo,As, at temperatures between 807 and 1050 K. AH:,
for the process is 54.26 f 0.7 kcal mol-l and AH&29sfor As,(@ is 45.45 f
0.7 kcal mol-l.
Reactions of (Me,Ge),AsH and the new germanium arsines M%GeAsHMe
and Me,GeAsHPh with Group IV dialkylamines are reported to give mixed
compounds such as (Me,Ge),AsSnMe,, Me,GeAsMeSnMe,, Me,Ge [As(GeMe,),],, and Me2Sn[As(G~M~,),],.~~
1.r. and n.m.r. data confirm the
formulations given.
Two new Ca-Si-As ternary phases, Ca,,Si7Asl, (monoclinic) and Ca,SiAs,
(cubic), have been identified.768The latter is unstable and decomposes to
Ca,As2 and the first compound. Preliminary investigations indicate that analogous phosphorus species can be obtained. The lead-rich portion of the
Pb-As system has been obtained.769The structure of VAs is similar to that
of MnP according to diffraction data,770and V4As, is isotypic with N ~ , A s , . ~ ~ ~
In TaSiAs, space group P4/nmm, each tantalum is surrounded by four
silicon and four arsenic atoms at the corners of a square antiprism in a
PbFC1-type structure.772
764
705
7G6
767
7G8
769
770
771
772
M. Baudler, B. Volland, and H. W. Valpertz, Chem. Ber., 1972,106,1049.

J. Garin and E. ParthC, Acta Cryst., 1972, B28, 3672.
J. J. Murray, C. Pupp, and R. F. Pottie, J . Chem. Phys., 1973,58,2569.
J. W. Anderson and J. E. Drake, J . Inorg. Nuclear Chem., 1973,35, 1032.
M. Guigueno, J. Guyader, and J. Long, Compt. rend., 1973, 276, C, 351.
S. E. Hutchinson and E. A. Peretti, J . Less-Common Metals, 1973, 30, 306.
K. Selte, A. Kjekshus, and A. F. Andresen, Acta Chem. Scand., 1972, 26,4057.
K. Yvon and H. Bolter, Monatsh., 1972, 103, 1643.
F. Hulliger, J. Less-Common Metals, 1973, 30, 397.
Elements of Group V
533
Improved data show that FeAs belongs to the space group Pnam or
Pr~a2,.~',
The Ni5As2phase, which has a small range of homogeneity, has a
complex structure according to X-ray data;774there are six different kinds
of nickel atoms surrounded by 8-10 other nickel atoms at distances between
2.44 and 3.05 A and three to five arsenic atoms at 2.27-2.78 A. The three
different kinds of arsenic atoms are each co-ordinated by ten nickel atoms.
Magnetic susceptibility and electrical resistivity have been measured over a
temperature range for the copper arsenidesCU+~AS,
CuS3As2, and C U , A S . ~ ~ ~
Neptunium diarsenide, formed by heating the hydride and arsenic in a
sealed tube at ca. 320 "C for a week, has a powder pattern that indicates a
Fe,As structure.776Heating the compound to 640 "C yields the monoarsenide, with a sodium chloride structure. Both plutonium776and amerimonoarsenides can be obtained from reactions of the hydride and
arsenic at ca. 320 "C.
Bonds to Carbon.-Arsenic(rrr) Compounds. Organoarsenic chemistry for

1971 has been reviewed.778Methyldichloroarsine reacts with diazomethane
to give the chloromethyl derivatives MeAs(CH,Cl)Cl and MeAs(CH,CI),,
and the action of nucleophiles on these compounds is described.779Ketoxime
esters of benzenearsonous acid, PhAs(0N: CR1R2),, can be obtained by the
reaction of PhAsO with k e t o x i m e ~while
, ~ ~ ~an alternative route from PhAsC1,
is also described.
1.r. and Raman data are reported for CF3AsH2 and the deuterium ana10gue,~~l
and the corresponding bis-derivatives (CF,),AsH and (CF,),AsD
have been prepared7*, for spectroscopic investigation.7s3 Treatment of
(CF,),AsI with Et3SiPH2gives the mixed arsino-phosphine (CF,),ASPH,,~~*
and reactions leading to cleavage of the As-P bond by reagents such as HBr,
Br,, and Me3SnH are described.7s5With P,F,, the product is (CF,),AsPF2.
A second arsino-phosphine results from reaction (8).7s6 The product is
2R3SiPH2
+ CF3As12
---f
2R2SiI
+ CF,As(PH&
(8)
readily oxidized and decomposes above -25 "C to CF,AsH, and polymeric
phosphorus hydride.
773
774
776
776
777
778
77s
780
781
783
78p
785
786
K. Selte and A. Kjekshus, Acta Chem. Scand., 1973, 27, 1448.

A. Kjekshus and K. E. Skaug, Acta Chem. Scand., 1973,27, 582.
L. J. Pauwels, G. Maervoet, and R. Vervaeke, 2. anorg. Chem., 1973,397, 307.
J. P. Charvillat and D. Damien, Znorg. Nuclear Chem. Letters, 1973,9, 337.
J. P. Charvillat and D . Damien, Znorg. Nuclear Chem. Letters, 1973, 9, 559.
G. 0. Doak and L. D. Freedman, J. Organometallic Chem., 1973, 48, 195.
M. Wieber and B. Eichhorn, Chem. Ber., 1973, 106, 2742.
R. G. Miftakhova, F. V. Akhmetova, and R. Kh. Sultanova, J . Gen. Chem. (U.S.S.R.),
1972,42,1960.
H. Burger, J. Cichon, R. Demuth, and J. Grobe, Spectrochim. Acta, 1973,29A, 943.
R. Demuth and J. Grobe, J . Fluorirte Chem., 1973, 2, 263.
H. Burger, J. Cichon, J. Grobe, and R. Demuth, Spectrochim. Acta, 1973,29A, 47.
R. Demuth and J. Grobe, J . Fluorine Chem., 1973, 2, 269.
R. Demuth and J. Grobe, J . Fluorine Chem., 1973, 2, 299.
R. Demuth and J. Grobe, Z . Naturforsch., 1973, 28b, 219.

There are no i.r. and Raman coincidences in the spectra of (CF,),AsAs(CF3)2, and it is concluded that the molecule exists in the trans (Cz,)
form in
the solid, liquid, and vapour states.787*788
The vibrational spectra of (CF,),As
have been analysed in detail to aid assignment of the diarsine spectra.ls7Mixed
Group IV arsines result from reaction between (CF,),AsH and Me,MPH,,
where M = Si, Ge, or Sn.789
Arsenic trifluoride in the presence of SbF, reacts with tetrafluoroethylene,
and both (C,F,),As and (C,F,),AsF were isolated.790No C2F5AsF2was
observed and it is concluded that the compound is unstable with respect to
reorganization to the observed products. On hydrolysis, (C,F,),AsF gives
the oxygen-bridged species (C,F5)2AsOAs(C2F5),.The reaction of diborane
with NaAsMe, parallels that previously reported for the phosphorus analogue
and gives Na[Me,As(BH,),] as
When this reacts further with
trimethylammonium chloride, the product is MqNBH,AsMe,BH,, and on
pyrolysis trirnethylamine borine is eliminated with formation of (128).
534
Carboxylic acid derivatives substituted by diphenylarsino-groups, e.g.

Ph,As(CH,),COX, are the products from reactions between NaAsPh, and
Cl(CH,).COX, where n = 1-3 and X = ONa, NH,, or OEt,792and diphenylarsine reacts with hexafluoroacetone to give P~,ASC(OH)(CF,),.~~~
cis- and trans-isomers of (129) in almost equal amount result from the
reaction of CF,Ci CCF, and the symmetrical diarsine M e P h A s A ~ p h M e , ~ ~ ~
but in hexafluoroacetone as solvent the cis-isomer predominates. meso- and
racemic forms of each isomer can be identified in the n.m.r. spectra, and complexes with Fe(CO), can be obtained. Two isomeric arsenic(v) species,
(CF,),M~AS[ON(CF,),]~, result when bis(trifluoromethy1)nitroxyl and
methylbis(trifluoromethy1)arsine react in a 2 :1 ratio.795
787
788
789
790
791
g2
793
794
795
J. W. Thompson, J. D. Witt, and J. R. Durig, Inorg. Chem., 1973,12,2124.

H. Burger, J. Cichon, R. Demuth, J. Grobe, and F. Hofler, 2. unorg. Chem., 1973,
396, 199.
S. Ansari, J. Grobe, and P. Schmid, J . Fluorine Chem., 1973, 2, 281.
B. Tittle, J . Fhorine Chem., 1973, 2, 449.
L. D. Schwartz and P. C. Keller, Inorg. Chem., 1973, 12,947.
A. Tzschach and W. Voigtlander, 2. anorg. Chem., 1973, 396, 39.
A. F. Janzen and 0. C. Vaidya, Cunad. J . Chem., 1973,51,1136.
W. R. Cullen and L. Mihichuk, Cunud. J . Chem., 1973,51,936.
H. G. Ang and W. S. Lien, J. Fluorine Chem., 1973,3,235.
Elements of Group V
535
A series of alkyldiphenylarsines have been synthesized from PhzAsCl
and the appropriate Grignard reagent.7961.r. data for the arsenic acetylene,
derivatives R;AsCiCR2, where R1 = Et, Pr, C5Hll, or C6H1, and R2 = H,
CO,Et, CO,H, etc., are interpreted as showing interaction between the Telectrons of the triple bond and the arsenic d - ~ r b i t a l sDiastereoisomers
.~~~
of
EtBunAs(C6H@,H) can be separated by fractional crystallization of the
morphine a d d u ~ tA. ~series
~ ~ of 10-alkylphenoxarsines (130) has been syn-
'
As
Ph
thesized from the corresponding chloride and organometallic reagent~.~Sg

Full details of the structure of 2,3,6,-triphenylarsenin (131) have now been
published.800
Arsenic(v) Compounds. On the basis of X-ray data, the compound obtained
by adding a solution of bromine in acetonitrile to Ph,As(OH)Br is formulatedsol as [Ph,As-OH
*
Br * * HO-AsPh,]+
Br;. In the cation the
As-0 and O-H
- . Br distances are 1.73(1) and 3.13(1) A, respectively,
and successive cations are linked by Br; ions which are slightly asymmetric.
1.r. and Raman data for (PhCH,),MX,, where M = As or Sb and X = F
or C1, are in accord with slightly distorted trigonal-bipyramidal geometry in
the solid state.802 Intramolecular ligand equilibration in five-co-ordinate
organo-bis(diphenyly1ene)arsines has been investigated by n.m.r. spectroscopy,*o3giving free energies of activation in the range 12-15 kcal mol-l.
1.r. and Raman data for methyl- and ethyl-arsonic acids RAsO,H, are discussedgo4in terms of C,symmetry for the skeleton, and strong peaks at 2820
and 2350 cm-l indicate that fairly strong hydrogen-bond formation occurs.
Data are also given for the alkali-metal saltsao5and the methyl and ethyl
esters.806The presence of a skeleton with C, symmetry is also the basis for
796
797
7s8
799
*03
SO5
SO6
R. D. Gigauri, G.-N. Chachava, B. D. Chernokal'skii, and M. M. Ugulava, J . Gen.

Chem. (U.S.S.R.),
1972, 42, 1530.
R. R. Shagidullin, I. A. Lamanova, L. A. Pavlova, and K. I. Kuz'min, Bull. Acad.
Sci. U.S.S.R.,Div. Chem. Sci., 1972, 21, 1652.
Yu. F. Gatilov, L. B. Ionov, and S. S. Molodtson, J . Gen. Chem. (U.S.S.R.),
1972,
42, 1527.
V. I. Gavrilov, V. N. Khlebnikov, G. R. Gavrilova, and B. D. Chernokal'skii, J.
Gen. Chem. (U.S.S.R.), 1972, 42, 1957.
F. Sanz and J. J. Daly, J.C.S. Dalton, 1973, 51 1.
M. Calleri and G. Ferguson, Cryst. Struct. Comm., 1972, I, 331.
L. Verdonck and G. P. van der Kelen, Spectrochim. Acta, 1973,29A, 1675.
D. Hellwinkel and B. Knabe, Phosphorus, 1972,2, 129.
A. Simon and H.-D. Schumann, 2.anorg. Chem., 1973,398, 145.
A. Simon and H.-D. Schumann, 2.anorg. Chem., 1972,393, 23.
A. Simon and H.-D. Schumann, 2.anorg. Chem., 1972,393,39.

interpreting vibrational data for the dimethyl- and diethyl-arsinic acids.807
These two compounds behave differently when treated with concentrated
hydrochloric acid, as vibrational data show that with the dimethyl compound
a hydrogen-bonded HCl adduct is formed while the ethyl analogue is able to
form the salt [Et,As(OH),]CI. The C,AsO; skeleton in the sodium and potassium salts of the two arsinic acids has C,, symmetry from spectroscopic
measurements.808
U.V. spectroscopy gives evidence for the protonated species PhAs0,H:
in aqueous perchloric acid solutions of phenyl- and substituted phenylarsonic a ~ i d s . Ionization-constant
8~~
data for a number of aromatic arsonic
acids enable the calculation of Hammett o-values for the substituents
-As03H2, -AsO,H-, and -ASO;-,~~O and pK values have been obtained
for solutions in dimethylformamide and dimethyl sulphoxide, showing that,
relative to water, the solvents have a differentiating action?ll
Phenylarsonic acid (L) displaces a thiourea ligand from Co(tu),Cl, to give
Co(tu)L,C1,812 and a number of CuII salts of substituted phenylarsonic acids
have been c h a r a c t e r i ~ e d The
. ~ ~ ~compounds have polymeric stuctures based
on octahedral co-ordination around the metal ion. Uranyl complexes
U02(XC6H4As03),~C,H50H,
where X = H, p-Me, p-MeO, p-cl, etc.,
recently obtained814have high melting points and low solubility, indicating
that these compounds are also polymeric.
Interaction between alkyl halides and trialkylarsine oxides generally yields
a hydrogen halide adduct, 2R,AsO,HX, with liberation of an olefin, but
with triethylarsine oxide and either methyl or benzyl iodide a hydroxy iodide
is produced.815A similar intermediate (132) has been isolated from experi536
(132)
ments on the rearrangement of the enantiomers of tertiary arsine oxides in

the presence of methyl iodide;*16the species finally decomposes to enantiomers
812
814
A. Simon and H.-D. Schumann, Z . anorg. Chem., 1973,400,294.

A. Simon and H.-D. Schumann, Z . anorg. Chem., 1973,399,97.
K. Vadasdi and I. Gaal, J. Inorg. Nuclear Chem., 1973,35, 658.
C. 6.Nualldin and S. 6. Cinnkide, J. Inorg. Nuclear Chem., 1973,35,2871.
V. M. Tsentovskii, V. S. Gamayurova, D. Sh. Zagidullina, and B. D. Chernokalskii,
J. Gen. Chem. (U.S.S.R.),
1972, 42, 2693.
M. M. Khan and A. U. Malik, J . Inorg. Nuclear Chem., 1973,35,247.
S. S. Sandhu, H. S. Kohle, and B. S. Manhas, Indian J . Chem., 1973, 11, 197.
S . Sandhu and G. S. Aulakh, Indian J. Chem., 1973, 11,46.
B. D. Chernokalskii and L. A. Vorobeva, J . Gen. Chem. (U.S.S.R.), 1972,42,2445.
Yu. F. Gatilov, L. B. Ionov, S . S. Molodtsov, and V. P. Kovyrzina, J. Gen. Chem.
(U.S.S.R.), 1972, 42, 1952.
Elements of Group V
537
of the corresponding arsinous esters. Basicity measurements for a number
of substituted phenarsazine oxides (133) show a relationship between the
(133)
ionization constant and the Hammett a-constant for the para-substituent

X.817
Bonds to Halogen.-E.s.r.
parameters are quoted for the radicals AsF; and
AsCl- roduced by y-irradiation of frozen polycrystalline AsF, and AsCI,,
3 P
respectively.818 The reaction of AsF, under pressure with Fe(CO), gives the
new compound A S ~ [ F ~ ( C O ) , ] ,which,
, ~ ~ ~ from single-crystal data, contains
an equilateral triangular arrangement of iron atoms. The arsenic atoms are
above and below this structure and each is equally bonded to the three iron
atoms (Fe-As = 2.35 A).
Liquid-vapour equilibria in the systems formed by arsenic trichloride
and its most probable impurities, i.e. S02C1,, SOCl,, PSCl,, and POCl,,
have been
showing that the latter two are the most difficult to remove by simple distillation. Substituted halogenoarsines react in the presence
of triethylamine with aldoximes to give the esters R ~ A S ( O N : C H R and
~)~
R;AS(ON:CHR~).~~~
1.r. and Raman studies have shown the formation of complexes between
tributyl phosphate and both arsenic and antimony tribromides.822Cryoscopy
in fused arsenic tribromide is reported for a number of inorganic and organic
solutes, showing 6T/6X2values lower than the ideal value,sz3and with dioxan
the compound 2AsBr3,3dioxan, melting at 64OC, is formed. Arsenic and
antimony trihalides give o-bonded transition-metal derivatives, such as
X,E[Fe(CO),(Cp)]:,
where E = As or Sb and X = C1 or Br, on reaction
with metal carbonyl anions or metal carbonyls with metal-metal bonds.824
The Hammett acidity function H, has been evaluated for a number of
superacid systems, including HSO,F-AsFS and HS03F-SbF,.825 The structure of the As,F,,O- ion in the dicaesium salt has been determined by X-ray
820
82z
823
824
825
G . Kh. Kamai, V. I. Gavrilov, and B. D. Chernokalskii, J. Gen. Chern. (U.S.S.R.),

1972,42, 1523.
S. Subramanian and M. T. Rogers, J. Chem. Phys., 1972,57,4582.
L. T. J. Delbaere, L. J. Kruczynski, and D. W. McBride, J.C.S. Dalton, 1973, 307.
L. A. Niselson, K. V. Tretyakova, and V. Ya. Akhmadeev, Rum. J . Inorg. Chem.,
1973, 18,576.
R. G . Miftakhova, S. G. Maksimenko, and Yu. I. KUSOV,
J . Gen. Chem., (U.S.S.R.),
1972, 42, 1963.
G. Roland, B. Gilbert, J. Decerf, and G. Duyckaerts, Spectrochim. Acta, 1973,
29A, 887.
R. C. Maheshwari, S. K. Suri, and V. Ramakrishna, Indian J. Chem., 1973,11,273.
W. R. Cullen, D. J. Patmore, and J. R. Sams, Inorg. Chem., 1973, 12, 867.
R. J. Gillespie and T. E. Peel, J. Amer. Chem. SOC.,1973, 95, 5173.
538
methods and shown to contain an As-O-As

As-0 distances
are 1.77(2) and 1.68(2) A and the bridge angle is 138.8', implying considerable
r-bond character; the As-F distances range between 1.68 and 1.80 A. In the
/"\
di-oxygen bridged species, (~YH')~(F~AS AsFd2-, the As-0
distance
O
'/
is 1.81 A and the OAsO and AsOAs angles are 84.0(4)' and 96,0(4)', respectively.828 The cation and anion interact through hydrogen-bond formation
(N-H - * - 0 = 2.86 A).
Mercury is oxidized by arsenic pentafluoride in liquid sulphur dioxide to
give H&(AsF&~,which contains a linear, centrosymmetric Hg$+ ion with
Hg-Hg distance of 2.552(4) A.829Evidence of the fluoride-ion-abstracting
ability of arsenic pentafluoride is shown by reactions with COFNSF2 and the
S-dichloride to give (0:C :NSF&+AsF; and (0:C :N :SCI,)+ASF;.~~~
The
compound XeF+Asq, obtained by oxidizing xenon with Cl,F+Asq, readily
loses AsF, to give X~FZASF;?~~
Bonds to Nitrogen.-A
number of dialkylaminodifluoroarsines R,NAsF,,
where R = Me, Et, Pr", or Bun; R2 = piperidine, morpholine, etc, result
from aminolysis of arsenic t r i f l ~ o r i d e The
. ~ ~ ~compounds were all characterized by i.r., n.m.r. , and mass spectroscopy. Mixed arsenic halides, which
rearrange to the homogeneous trihalides, are considered to be the initial
products when Et2NAsF2 reacts with hydrogen halides.833 Spectroscopic
evidence points to the nitrogen atom in Me2NAsF, as the donor site in the
1 :1 adduct with boron trifluoride,834but in the borine adduct the co-ordination site seems to be the arsenic atom.
Ten bis(dia1kylamino)-derivatives have been prepared from MeAsI, and
c h a r a c t e r i ~ e dand
, ~ ~ ~cleavage of the A s N bond is shown to occur on reaction with H,O, ROH, RSH, and HX. Transamination reactions between
dimethylaminodimethylarsineand secondary amines provide a convenient
route to other Me2AsNR2species, and data are presented for eleven such
derivatives.836Magnetic susceptibility, refraction, and lH n.m.r. data have
been obtained for the compounds in the series X,,AsCl,,
where X = NR,,
OR, or R, showing in the former back-co-ordination from nitrogen to
arsenic.837
826
828
829
830
831
832
833
834
835
836
837
W. Haase, Ber. Bunsengesellschaft phys. Chem., 1972, 76, 1000.

W. Haase, Z . anorg. Chem., 1973,397, 258.
W. Haase, Chem. Ber., 1973, 106, 734.
B. D. Cutforth, C. G. Davies, P. A. W. Dean, R. J. Gillespie, P. R. Ireland, and P. K.
Ummat, Inorg. Chem., 1973, 12, 1343.
R. Mews, 2.Naturforsch., 1973, 28b, 99.
K. 0. Christe and R. D. Wilson, Inorg. Nuclear Chem. Letters, 1973,9,845.
F. Kober, J. Fluorine Chem., 1973, 2 , 247.
F. Kober, Z . anorg. Chem., 1973, 398, 115.
J. G. Morse and K. W. Morse, Inorg. Chem., 1973,12,2119.
F. Kober, Z . anorg. Chem., 1973, 397, 97.
F. Kober, 2.anorg. Chem., 1973, 400,285.
M. Durand and J.-P. Laurent, Bull. SOC.chim. France, 1973,2169.
Elements of Group V
539
A new method for preparing triphenylarsinimines Ph,As=NX, where
X = Ph, CN, Bz, CO,Et etc., from triphenylarsine and azides (XN,) under
nitrene-producing conditions has been reported.838The compounds also
result when triphenylarsine reacts with amides in the presence of lead tetraacetate, probably via Ph,As(OAc), as an intermediate.
Bonds to Oxygen.-Kinetic data on the oxidation of arsenic(rI1) by vanadium(v)

indicates39 that the reaction proceeds uia an arsonium ion of the type
(HO),As=O rather than an intermediate complex, as found for the reaction

with chromic acid. Cyclic esters, e.g. (134), can be obtained from arsenic
trichloride and 2,2-dihydro~ybiphenyl,~~~
and when the reaction with pyro-
(134)
catechol, for example, is carried out in the presence of triethylamine, complete chlorine replacement occurs to give (135). Spiro-compounds (136)
result from the selenium dioxide oxidation of the cyclic arsenic(rr1) esters
(137),s41but if the reaction is carried out in the presence of 1,2-diols it is
(136) R = H or Me
(1 37)
possible to isolate the unsymmetrical derivatives (138). lH n.m.r. data for the
arsolans (139) have been analysed in detail to give the stereochemistry of the
ring system, and evidence is presented for rapid pseudorotation in these
systems.842
Vibrational data for the esters As(OR), and As(SR), show that v(As-0)
falls between 575 and 699cm-l, while v(As-S) is in the region 345-437
838
839
840
841
842
J. I. G. Cadogan and I. Gosney, J.C.S. Chem. Comm., 1973, 586.

B. B. Pal, D. C. Mukherjee, and K. K. Sengupta, J. Inorg. Nuclear Chem., 1972, 34,
3433.
K. Andra and L. Martschei, Z . anorg. Chem., 1973, 396, 123.
M. Wieber, B. Eichhorn, and J. Gotz, Chem. Ber., 1973, 106, 2738.
D. W. Aksens and 0. Vikane, Acta Chem. Scand., 1973,27, 1337.
540

HSC-Y
\As4
HiC-X /
(139) R = PhorC1
X = Y = O o r S
x = 0,Y = s
cm--1.843The corresponding deformation modes occur at 328-394 and 230296 cm-l, respectively. Data for the analogous antimony compounds are also
presented. The most intense ion in the mass spectra of these corn pound^^^^*^^
is As(XR)$, and by comparison with the phosphorus analogues it appears
that arsenic is less capable of achieving multiple bonding to other atoms.844
Force constants have been calculated from vibrational data for MqAsO,
(Me0)3A~,and ( M ~ O ) , A S O .l ~H~ n.m.r.
~
spectra for solid samples of
AsO(H,PO,), As,O,(HPO,), and As,O,(HAsO,) have been reported.846
An excess of boiling trifluoroacetic anhydride reacts with sodium arsenite
to give the compound NaAsO(CF,CO,), in good yield:*' and similar bismuth
reactions also take place. Polarographic and potentiometric measurements in
aqueous solution point to the formation of a complex [As(OH),HX]between arsenic(II1) and nitrilotriacetic acid (H3X).848
The structure of the arsenic-tartrate anion in a complex cobalt salt, shown
in Figure 12, consists of two arsenic atoms linked by two quadridentate
U
As (1)
Figure 12 Co-ordination about the two arsenic atoms in the arsenic-( +)tartrate anion
(Reproduced by permission from Bull. Chem. Soc. Japan, 1973,46,2424)
843
044
*45
846
847
848
T. B. Brill and N. C. Campbell, Inorg. Chem., 1973, 12, 1884.

P. Freyen and J. Meller, Org. Mass Spectrometry, 1973,7,73.
I. A. Lamanova and R. R. Shagidullin, Bull. Acad. Sci. W.S.S.R.,
Div. Chem. Sci.,
1972,21,2607.
C. DorCmieux, M. Krahe, and F. d'Yvoire, Bull. SOC.chim. France, 1973,409.
P. V. Radheshwar, R. Dev, and G . H. Cady, J . Znorg. Nuclear Chcm., 1972,34,3913.
N. G. Elenkova and R. A. Tsoneva, J. Inorg. Nuclear Chem., 1973.35,841.
Elements of Group V
541
tartrate ions, with As-0 bonds of 1.80 and 2.04 A to alcoholic and carboxylic oxygens, respectively.849The arsenic atom in K( -),,-tris(benzene1,2-diolato)arsenate(v),l .5Hz0is approximately octahedrally co-ordinated
(see Figure 13), with a mean As-0 distance of 1.84 A, and OAsO and AsOC
angles of 87.0 and 1loo, respectively.850The absolute configuration, determined by the absorption edge technique, is in agreement with c.d. spectra,
Figure 13 The structure of the tris(benzene-1,2-diolato)arsenate(v) anion,

showing the absolute con$guration
and the isomer is designated as A. Complexes containing the arsenate ion,

e.g. [Co(NH3),HAs04]+and [Co(NH3),H,As0,J2+, have been prepared and
the lability of the oxygen atoms has been examined.851
E.s.r. studies of irradiated ferroelectric KH,AsO, and KD,AsO,, and of
antiferroelectric NH,H,AsO, and ND4D2As04,have been used to investigate
the effects on lattice properties of the presence of AsOF radicals.852From
Bps
850
851
852
K. Matsumoto, H. Kawaguchi, H. Kuroya, and S. Kawaguchi, Bull. Chem. SOC.

Japan, 1973,46,2424.
A. Kobayashi, T. Ito, F. Marumo, and Y. Saito, Acta Cryst., 1972, B28,3446.
T. A. Beech, N. C. Lawrence, and S. F. Lincoln, Austral. J . Chem., 1973,26,1877.
B. Lamotte, J. Gaillard, and 0. Constantinescu, J. Chem. Phys., 1972,57,3319.
542

X-ray data, both
and M~(NH,)AsO,,GH,O~~~
are
isostructural with the phosphorus analogues, and in each compound the
structural units are octahedral Mg(OH&+ and tetrahedral As0;- units. In
the former compound the seventh water molecule is linked by hydrogen
bonds only, and the acidic proton is involved in the formation of symmetrical
hydrogen bonds. The calcium salt CaHAs04,3H20is isostructural with newberryite and consists of layers of CaO, octahedra and AsO, tetrahedra connected by zigzag chains of hydrogen bonds.856
Solubility studies point to the existence of the hydrated double arsenates
NaCaA~0~,7.5H,O,8~~
NaSrA~0,,9H,0,8~*and NaBaA~0,,9H,0,8~~
and
their dehydration has been followed by t.g.a. From X-ray data the potassium
and calcium ions in KCaAs0,,8H20 are each co-ordinated to eight oxygen
atoms at the corners of a square antiprism, and each oxygen of the arsenate
ion is the acceptor in hydrogen-bond formation with four water molecules.859
A scandium arsenate SC,(HASO,)~,~H,Ohas been prepared which gives
the anhydrous material on heating to ca. 210 0C.860On further heating this
decomposes to Sc,(As,O,), and finally, at 87OoC, ScAsO, is obtained.
FeAs0,-I has been shown to have a monoclinic unit
and the structure
of mercury@ orthoarsenate is built from Hg:+ and As0;- ions such that
three of the oxygen atoms are linked to different mercury units.862The
mercury atoms are effectively four-co-ordinate from three oxygen atoms and
the second mercury atom; the 0-Hg-Hg-0
unit departs significantly from
linearity. The naturally occurring hydrated Zn(UO,),(AsO,), crystallizes in
the tetragonal space group P4,/m, with a = 7.16 and c = 17.20 kse3
In the diarsenate Na4As,0,, the anion consists of two AsO, tetrahedra
sharing an oxygen atom, with the bridge angle AsOAs equal to 123.5' and
As-0 distances of 1.783 A. The average value for the terminal oxygenarsenic distance is 1.658 A.864
Bonds to Sulphur or Selenium.-Gas-phase laser Raman spectra of mixed
arsenic-sulphur vapours
that the arsenic-rich mixtures contain As4,
AS&, As$,, and As$,. Far4.r. and 12'1 and 75Asn.q.r. spectra for As,S3
and AsSI and the selenium analogues have been measured.866
853
854
855
856
857
858
859
860
861
862
863
864
865
866
G. Ferraris and M. Franchini-Angela, Acta Cryst., 1973, B29, 286.

A. Whitaker, Z . Krist., 1973, 137, 194.
G. Ferraris and M. Franchini-Angela, Acta Cryst., 1973, B29, 859.
M. Catti and G. Ferraris, Acta Cryst., 1973, B29, 90.
N. Ariguib-Kbir and H. GuCrin, Bull. SOC.chim. France, 1973, 863.
N. Ariguib-Kbir and H. GuCrin, Compt. rend., 1973, 276, C,767.
B. Dickens and W. E. Brown, Acta Cryst., 1972, B28, 3056.
N. P. Khrameeva, G. Ya. Pushkina, L. N. Komissarova, and E. G. Teterin, Russ.
J. Inorg. Chem., 1973, 18,455.
F. d'Yvoire, Compt. rend., 1972,275, C, 949.
B. Kamenar and B. Kaitner, Acta Cryst., 1973, B29, 1666.
H. Agrinier, F. Chantret, J. Geffroy, and B. HCry, Bull. SOC.
franc. MinJrale Crist.,
1972, 95, 360.
K. Y. Leung and C. Calvo, Canad. J. Chern., 1973, 51, 2082.
A. Rogstad, J . Mof. Structure, 1972, 14, 421.
E. V. Bryukhova, A. P. Chernov, S. A. Dembovskii, and G. K. Semin,J . Struct. Chem.,
1972,13,493.
Elements of Group V
543
,8-Dimorphite, As,$ (140), has C,, symmetry, as found previously for the
a-modif~cation.~~~
The As-S distances have a mean value of 2.23 8, and the
(140)
unique SAsS angle is 98.5'. Three 75Asn.q.r. resonances are observeds68for

both the a- and B-forms corresponding to the three non-equivalent sites
[see (140)]in the unit cell, and the difference between the values for the two
forms is due to electrostatic field-gradient effects.
Refinement of the realgar, As4S4,and orpiment, AS&, structuresS69confirms the original structures. The mean As-S distance in the cradle-like
structure of Asps4is 2.237(2) A while the As-As distances are 2.57A. The
SAsS angles range between 94.5 and 95.1' and the AsSAs angles have values
between 100.8 and 101.3".The orpiment structure consists of layers formed
from As-S-As-S
chains linked together by sulphur bridges between arsenic atoms; As-S distances vary between 2.243 and 2.308 A. The existence
of a @-formof Asps4with higher symmetry than the a-(realgar) form is confirmed by 75As n.q.r. and far4.r. spectroscopy.870The structure of As4S,,
which can be obtained by slow evaporation of a solution of As$, in carbon
disulphide, is shown in (141).871The molecule has ca. C,, symmetry, with
As-S and As-As distances of 2.24 and 2.55 A, respectively.
The lH n.m.r. spectrum of 2-chloro-l,3,2-dithia-arsenan(142) has been
analysed and shown to be consistent with the predominance of one of the
possible chair ~ o n f o r m e r s . 8(see
~ ~ ~also ref. 842). The As-S bonds in arsenic(111) thioacids, e.g. PhAs(SBun)2and PhAs(SEt),, are broken by halogens and
a number of non-metal halides to give P ~ A S X , . ~ ~ ~ ~
867
868
870
871
87=
H. J. Whitfield, J.C.S. Dalton, 1973, 1739.

T. J. Bastow, I. D. Cambell, and H. J. Whitfield, Austral. J. Chem., 1972,75,2291.
D. J. E. Mullen and W. Nowacki, Z. Krist., 1972, 136, 48.
T. J. Bastow and H. J. Whitfield, Solid State Chern., 1972, 11, 1015.
(a) D. W. Aksnes and 0. Vikane, Acta Chem. Scand., 1972, 26, 4170; (b) N. A.
Chadaeva, G. Kh. Kamai, and K. A. Mamakov, Bull. Acad. Sci. U.S.S.R., Div.
Chern. Sci., 1972, 21, 1552.
544
W
(141)
Arsenic(II1) tris(dithi0carbamates) As [SC(S)NR,], result when arsenic

trichloride reacts with amines and carbon d i s ~ l p h i d e ,and
~ ~ ~analogous
antimony compounds can also be obtained. The reaction is considered to
proceed by CS2insertion into the As-N bonds of the trisamino-derivatives
and the products are considered to have an octahedral arrangement around
arsenic which is distorted owing to the effect of the lone pair. The compounds
show benzene-induced lH n.m.r. solvent shifts, probably as a result of the

formation of 1:1 van der Waals c0mplexes.8~~
The dithio-salt Me,As(S)SNa
results when sodium cacodylate reacts with hydrogen ~ u l p h i d e , ~and
'~ a
number of metal derivatives have been prepared and investigated.
The reaction between zinc or cobalt perchlorate and Me,As(S)SAsMe,
gives a product with the stoicheiometry M4S13As,Me,,, and single-crystal
data for the zinc compound show that the structure is analogous to that of
basic beryllium a~etate.8'~
Four zinc atoms lie at the corners of a tetrahedron,
with a sulphur atom at the centre, and the zinc atoms are bridged by six
Me2AsS2groups. Tertiary arsine sulphides react with acetyl chloride, yielding
arsonium chloride derivatives>77e.g. [R,AsSCOMe]+Cl-, which on heating
lose RCl to give acetylthio-arsinesR2AsSCOMe.
873
874
875
G. E. Manoussakis and C. A. Tsipis, J. Inorg. Nuclear Chem., 1973, 35, 743.

G. E. Manoussakis and C. A. Tsipis, 2. anorg. Chem., 1973,398,88.
W. Kuchen, M. Forster, H. Hertel, and B. Hohn, Chem. Ber., 1972, 105, 3310.
D. Johnstone, J. E. Fergusson, and W. T. Robinson, Bull. Chem. SOC.Japan, 1972,
45, 3721.
877
Yu. F. Gatilov, V. A. Perov, and M. G. Kralichkina, J. Gen. Chem. (U.S.S.R.),

1972,42,2458.
Elements of Group V
545
Evidence has been presented for the preparation of pure samples of
Na,AsO,S,,l 1H,O and Na,AsS4,8H,0.s78 The structure of the mineral
lorandite, T12As,S4, contains spiral chains of ASS, pyramids connected by
thallium atoms.s79
The structure of As4Se4,shown in (143), is similar to that of cr-realgar, with
symmetry close to
and As-As and As-Se distances of 2.56 and 2.39 A,
respectively.880~ss1
X-Ray data for polycrystalline samples of As,Se, and
As,Se, have also been obtained.8s2Compounds with the formulae Ag3AsSe3,
Ag,AsSe,, and AgAsSe2have been identified in a study of the liquidus of the
ternary Ag-As-Se system.s83
4 Antimony
General.-Mass spectrometric data have been used to obtain dissociation

energies and the standard heats of formation for Sb,, Sb,, Sb,, SbP, and
SbP3.884The crystal structure of Sr,Sb is similar to the PbFCl structuress5
and contains strontium atoms with co-ordination numbers of 12 and 13;
the antimony atoms have nine strontium atoms as near neighbours. The
average Sb-Sr distance is 3.499& which is shorter than the sum of the
metallic radii. Evidence in favour of predominantly covalent bonding in the
~.,.*$3* b, ,886a RhSb,,
skutterudite-type binary antimonides C O S ~ , , ~Fe,~,. ~5Ni,
878
879
880
881
883
M. Palazzi and H. Gutkin, Bull. SOC.chim. France, 1973, 851.

M. E. Fleet, 2. Krist., 1973, 138, 147.
T. J. Bastow and H. J. Whitfield, J.C.S. Dalton, 1973, 1739.
E. J. Smail and G. M. Sheldrick, Acta Cryst., 1973, B29, 2014.
A. L. Renniger and B. L. Averbach, Actu Cryst., 1973, B29, 1583.
I. S. Kovaleva, Z. S. Medvedeva, and S. A. Tarasevich, Russ. J. Inorg. Chem., 1972,
17, 1622.
J. Kordis and K. A. Gingerich, J . Chew.. Phys., 1973, 58, 5141.
asti M. Martinez-Ripoll, A. Haase, and G . Brauer, Acta Cryst., 1973, B29, 1715.
(a) A. Kjekshus, D. G. Nicholson, and T. Rakke, Acta Chern. Scand., 1973, 27,
1315; (b) A. Yu. Aleksandrov, S. K. Kovaleva, R. N. Kuzmin and V. D. Romashov,
546
and IrSb, comes from recent 121Sb Mossbauer data.886X-Ray photoelectron
spectra are reported for SbF,, KSbF,, Sb205,Sb,S,, etc., and for a number
of bismuth compounds.887
Organo-antimony chemistry for 1971 has been surveyed.88sThe preparation
of (Ph3Sb)20(C10,)2has been re-examined and the product shown to be a
dihydrate which can be converted into the anhydrous material by treatment
with triethyl o r t h ~ f o r m a t e The
. ~ ~ ~analogous methyl compound does not
form a hydrate. 1.r. data suggest that the hydrated phenyl compound probably
has an ionic structure, but a non-ionic, five-co-ordinate, structure analogous
to that found for the bismuth compound is suggested for the anhydrous
compound. The methyl and phenyl compounds, on treatment with ligands
such as dimethylacetamide, dimethyl sulphoxide, and triphenylphosphine
oxide, give cationic complexes of the form [(R,SbL)20]2f(C10;),. Pure
triphenylantimony oxide, melting at 222 'C, is partially associated in the solid
but monomeric in benzene, and it can be prepared by thermolysis of hydroxytetraphenylantimony inp-xylene solution or by hydrolysis of Ph,Sb(OMe)2.sg0
Refluxing the compound in xylene in the presence of oxygen gives diphenylstibinic anhydride, Ph,Sb(O)OSb(O)Ph,.
Bonds to ~alogen.-Anrimony(IrI) Compounds. Vapour-pressure data and
values of the sublimation enthalpy have been obtained for antimony trifluoride and bismuth trifluoride, using a method based on differential calorimetry combined with the Knudsen effusion technique.891 The vapourpressure equations for SbF, and BiF, are, respectively:
log,, (plTorr) = 11.48 f 0.06
- 5176 f 23/(T/K) (375-455
K)
log,, (p/Torr) = 11.79 f 0.09 - 9797 f 70/(T/K) (669-838 K)

The Raman spectrumsg2of crystalline SbF, contains six principal lines in the
region between 495 and 200 cm-l.
Raman data for solid and molten antimony trichloride can be interpreted
on the basis of discrete molecules with C,, ~ymmetry,8~~
and the changes which
occur on addition of potassium chloride to the melt do not indicate the formation of appreciable amounts of SbCl,. Addition of AlCl, does not lead to
bands characteristic of the AlC1; ion, but interaction of some kind certainly
occurs, to give perhaps the polymeric species (SbCl,,AlCl,),. Heat capacities
have been determined for SbCI, (35.2 cal K-l mol-l) and SbBr, (34.6 cal
887
888
889
891
8D2
893
W. E. Morgan, W. J. Stec, and J. R. Van Wazer, Inorg. Chem., 1973,12,953.

L. D. Freedman and G . 0. Doak, J . Organometallic Chem., 1973, 48,258.
R. G . Goel and H. S. Prasad, Inorg. Chem., 1972,11,2141.
W. E. McEwen, G . H. Briles, and D. N. Schulz, Phosphorus, 1972, 2, 147.
G . de Maria, L. Malaspina, G . Bardi, and R. Gigli, Rev. Roumaine Chim., 1973, 18,
367.
V. V. Fomichev, K. I. Petrov, and L. A. Sadokhina, Russ. J. Inorg. Client., 1972,
17, 1348.
K. W. Fung, G . M. Begun, and G . Mamantov, Inorg. Chem., 1973, 12,53.
Elements of Group V
547
K-l mol-l),ss4 and electron-diffraction measurements give r(Sb-Cl) =
2.333(3) A and LClSbCl = 97.2(9)' and r(Sb-Br) = 2.490(3) A and
LBrSbBr = 98.2(6)', respectively, for the trichloridesg5and t r i b r ~ m i d e . ~ ~ ~
The latter can be prepared rapidly and simply by a reaction between acetyl
bromide and antimony pentachloride in carbon t e t r a c h l ~ r i d e In
. ~ ~the
~ early
stages an intermediate CH,COBr ,SbC15 precipitates.
Antimony(1Ir) and bismuth(II1) fluorides give the adducts SbF,,SbF, ,
SbF,,AsF, , BiF,,3SbF5, and BiF,,AsF, on treatment with the required
pentahalide in liquid sulphur dioxide.8s8The second of these can also be obtained when elemental antimony reacts with arsenic pentafluoride, but with
antimony pentafluoride an alternative form of SbF,,SbF, results. The compound BiF3,3SbF5can be formulated as Bi(SbF,),, but spectra indicate extensive fluorine-bridging between the cation and the anion. Raman spectra
suggest that the other compounds have similar structures, with possibly
fluorine-bridged polymeric cations.
Mixed antimony(II1) sulphate fluorides with compositions M2S04,2SbF3,
3M2S04,4SbF3,and M2S04,SbF3can be obtained by evaporating aqueous
solutions of the trifluoride and Group I s u l p h a t e ~ . *Crystal-structure
~~
determinations have been reported for both the M-900
and L-formsgol of
SbOF. In each case the antimony atom is surrounded by three oxygen atoms
and one fluorine in such a way that with the lone pair of electrons the arrangement is trigonal-bipyramidal. In the M-form these units share edges to form
layers parallel to the ab plane, while in the latter the antimony polyhedra
form endless chains in the b-direction.
Crystals of compounds with Sb,O,:SbI, ratios of 14:2, 11:2, and 8:2,
i.e. Sb,O,I, Sb8OI1I2,and Sb,O,I, have been obtainedso2by vapour transport,
and X-ray measurements indicate that at least two other species with higher
SbI, content exist. Incongruently melting compounds 3TICl,SbCI,,
2T1C1,3SbC13, and 2TlCl,SbCI, have been observed in a d.t.a. study of the
TICI-SbC1, system;s03the diagrams with PCl, and FeCl, showed eutectics
only, and CCI,, TiCl,, and ZnCI, were not miscible with antimony trichloride.
Changes in the position of the 'most intense' M-Cl band in a series of
antimony chloride species, including SbCI,, SbCIk, Me2SbC1,, Me2SbC1y,
and SbClr, have been discussed in terms of the effect of the lone pair and the
methyl group on bond lengthsnW4
The chemical shift in the 121SbMossbauer
K. Takeyama and T. Atoda, Bull. Chem. SOC.Japan, 1972,45,3078.
S . Konaka and M. Kimura, Bull. Chem. SOC.
Japan, 1973,46, 413.
SS6 S. Konaka and M. Kimura, Bull. Chem. SOC.
Japan, 1973,46,404.
G. Goetz and M. J. F. Leroy, Compt. rend., 1973,276, C, 1719.
898 T. Birchall, P. A. W. Dean, B. D. Valle, and R. J. Gillespie, Canad. J. Chem., 1973,
51, 667.
8 9 9 R. L. Davidovich, L. A. Zemnukhova, andN. I. Sigula, Rum. J . Inorg. Chem., 1973,
18, 73.
A. Astrom, Acta Chem. Scand., 1972,26, 3849.
$01 A. Astrom and S. Andersson, J . Solid-state Chem., 1973, 6, 191.
902 V. Kramer, M. Schuhmacher, and R. Nitsche, Materials Research Bull., 1973, 8,65.
903 N. D. Chikanov, Russ. J . Inorg. Chem., 1973, 18, 148.
I. R. Beattie, F. C. Stokes, and L. E. Alexander, J.C.S. Dalton, 1973, 465.
894
8Q5
36
548
spectra of SbX; species increases in the order Cl < Br < I, which is the order
of increasing covalent character;w5data are also given for a number of mixed
halides etc.
The crystal structure of 2-picolinium tetraiodoantimonate(rI1) consists of
infinite chains with approximately octahedral co-ordination of iodine atoms
around antimony,go6and octahedral co-ordination is similarly present in bispiperidinium pentabromoantimonate(~r~).~~~
In the latter, the bridging SbBr distances are 3.016(3) and 3.125(3) A, while the terminal bonds vary
between 2.570(3) and 2.828(2) A. The structure is analogous to the previously
examined bismuth compound, and a noticeable feature of the two structures
is the close similarity between Bi-Br and Sb-Br bridging distances.
Crystal data show the presence of isolated SbFg- ions with approximately
square-pyramidal geometry in the structure of (NH,),SbF,.908 The apical and
basal Sb-F distances are 1.916(4) and 2.075(2) A, respectively, and the antimony lies 0.38 A below the plane of the basal fluorines. The stereochemical
activity of the lone pair in :MX, species, where M = Sb, Te, I, or Xe, is
discussed. The anion structure in Co(NH,)FSb2e is best described in terms
of two distorted octahedra sharing a corner (144);909the Sb-F bridge dis-
(144)
tances are markedly different (2.249 and 2.449 A) and the angle at the bridge
is 142.1'. The other Sb-F distances vary, with that trans to the lone pair
being the shortest (1.948 A) followed by that trans to the bridge (2.015 A).
The compound (Me4N),Sb2Brll contains Sb,Brr ions and Br, molecules
linked together to give a three-dimensional network,g10but the anion structure
is markedly different from that discussed above for the fluoride. The overall
symmetry is D,, and results from face sharing by two SbBr6 octahedra. The
bridge distances are 3.04 A, compared with terminal Sb-Br bonds of 2.63 A,
and the SbBrSb bridge angle has a value of 79.6O; the Br-Sb-Br
- - Br-Br - chain is approximately linear.
Raman and i.r. data for M,SbCl,, K2SbCI5,Rb$b3C1,,, Cs5Sb,C1,,, and
Cs,SbCl, are interpreted to imply octahedral co-ordination around the antimony and the formation of Sb-C1-Sb
bridges,911 and similar structures are
005
Oo6
90'
010
911
J. D. Donaldson, J. T. Southern, and M. J. Tricker, J.C.S. Dalton, 1972,2637.

H. A. Abdel-Rehim and E. A. Meyers, Cryst. Struct. Comm., 1973, 2 , 121.
H. A. Abdel-Rehim and E. A. Meyers, Cryst. Struct. Comm., 1973, 2 , 45.
R. R. Ryan and D. T. Cramer, Znorg. Chem., 1972, 11, 2322.
D. R. Schroeder and R. A. Jacobson, Znorg. Chem., 1973,12,515.
C . R. Hubbard and R. A, Jacobson, Inorg. Chem., 1972, 11, 2247.
V. V. Fomichev, K. I. Petrov, G. V. Zimina, and V. E. Plyushchev, Rum. J. Inorg.
Chem., 1973, 18,220.
Elements of Group V
549
postulated for M3Sb2Brgand M,Sb3Br16 species.g12Raman spectra of aqueous
solutions of antimony(xI1) in a range of concentrations of HBr and HI are
interpreted in terms of two species only for the former; i.e. SbBrk for Br: Sb
ratios greater than six and SbBr5(H,0)2-.g13 In the iodide system similar
species are present, together with a third which is tentatively identified as
SbIE-; there was no evidence for either SbX; or SbX:--n, where n > 6 . 1.r.
and Raman spectra of S b X t and Six:- compounds together with the corresponding pentabromide and pentaiodide anions have been investigated to
assess the influence of the lone pair.914Data are presented to show that the
SbBrz- ion in the piperidinium salt is a discrete species with C,, symmetry,
while data for SbX, in solution are discussed in terms of C,, symmetry.
Antimony(v) Compounds. To resolve ambiguities concerning the relative

amounts of polymeric species in the vapours of the Group V pentafluorides,
saturated vapours of the compounds have been re-examined using a molecular
beam source mass spectrometer.915No association was observed for PF, or
AsF,, but for SbF, the ratio of monomer:dimer:trimer was 1 :0.5:0.09, and
in addition, traces of the tetramer and pentamer were observed. Bismuth
pentafluoride gave a cracking pattern different from that reported previously,
and in addition to considerable amounts of dimer ions, the Bi,F;', and Bi3F&
ions were detected. The reaction between antimony pentafluoride and either
C1,O or C102gives chlorine and the compound C102SbF,, but with an excess
of SbF,, i.r. and X-ray data show that ClO,,Sb3F16 is also produced.g16No
evidence could be obtained for the previously reported C102SbF,. The reaction with C1206can be represented by the equation:
ClaOe
+ 2SbF5
+ ClOISbFd
+ SbOF, + ClOsF
Liquid-vapour and liquid-solid equilibria in the SbF,-UF6 and SbF,-MoF,

systems have been in~estigated.~~'
The complex species XeF; SbF;, XeFL, Sb,F;, and XeOFi SbF; have
been prepared,918and with mercury in liquid sulphur dioxide SbF, gives
Hg3(Sb2F11),.829The pentafluoride will convert isobutane into the carbonium
ion C,H: Sb2F;;,9l9and a number of polynuclear aromatic hydrocarbons have
been oxidized by SbF, to dipositive ions.920Methylmalonic acid and its
derivatives are converted by SbF5-HS03F mixtures into the methylketenylacylium ion MeC( :C:O)(C :O)f.g21
K. I. Petrov, V. V. Fomichev, L.L. Kochergina, G. V. Zimina, and V. E. Plyushchev,
Russ. J. Inorg. Chem., 1973, 18, 523.
Q13 M. A. Hooper and D. W. James, J. Inorg. Nuclear Chem., 1973, 35, 2335.
91* M. A. Hooper and D. W. James, Austral. J . Chem., 1973, 26, 1401.
915 M. J. Vasile and W. E. Falconer, Inorg. Chem., 1972, 11,2282.
916 Z . K. Nikitina and V. Ya. Rosolovskii, Bull. Acad. Sci. U.S.S.R., Div. Chem. Sci.,
1973,21,265.
917 V. K. Ezhov, Russ. J . Inorg. Chem., 1972, 17, 1059.
Dl8 D. E. McKee, C. J. Adams, and N. Bartlett, Inorg. Chem., 1973,12,1722.
9l9 J. Lukas, P. A. Kramer, and A. P. Kouwenhoven, Rec. Trau. chim., 1973,92,44.
s 2 O D. M.Brouwer and J. A. van Doorn, Rec. Trau. chim., 1972,91, 1110.
921 K. Conrow and D. L. Morris, J.C.S. Chem. Comm., 1973,s.
912
550

The crystal structure of the NbF,,SbF, adduct shows an endless zigzag
chain of alternating niobium and antimony atoms linked by asymmetric cis
fluorine
and a distorted octahedral arrangement around each atom
is completed by four terminal fluorine atoms. Bridge bond lengths are 1.95
and 2.17 A, respectively, for antimony and niobium while the terminal distances are all 1.81 A; the NbFSb bridge angle is 163.5'. The data indicate a
substantial contribution from the ionic form NbFiSbF;, showing that SbF,
is a better fluoride-ion acceptor than the niobium compound. In Cs2[Sb,F,,,0]
the anion has C2symmetry and consists of two octahedral units linked by an
oxygen bridge. The Sb-0 distance and SbOSb angle are 1.88 A and 136.2',
respectively, while the mean Sb-F distance is 1.87 A.923A trimeric species
Sb3FI2Okhas also been investigated.82s
lH n.m.r. measurements show that in dichloromethane solution a monomeric adduct is formed between water and antimony pentachloride at ratios
less than 1 :l.924
At higher water ratios, a second molecule is added to form,
probably, a hydrogen-bonded dihydrate. Conductivity in the SbCI,-H,PO,
system does not involve ionization of the 1 :1 adduct according to experiments
involving radioactive
and the data can be explained solely in terms
of conductivity by the free phosphoric acid present. 1.r. and Raman data for
SbF5,CH3CN and the deuterium- and 15N-substitutedspecies are in accord
with C,, symmetry for the SbF,N moiety.926 N.q.r. measurements on
ClCN,SbCl, are markedly different from those found for the acetonitrile
adductgZ7and are considered to be associated with a significant increase in the
electronic charge associated with the chlorine atoms and a decrease in the
electric quadrupole at the antimony atom.
NN-Dimethylcarbamoyl chloride, Me,NC(O)CI, and the N-methyl compound both form 1 : l adducts via the oxygen atom with SbC15,928but the
latter slowly loses hydrogen chloride. Similar compounds result with carbamoyl a z i d e ~but
, ~ ~in~the presence of hydrogen chloride the oxygen atom is
protonated and hexachloroantimonates (145) result. Structural data on SbCI,,
(145)
C&&OC1 and the adduct with m-CH,C,H,COCI indicate that the antimony
is surrounded octahedrally by five chlorine atoms (mean Sb-Cl = 2.319)
A. J. Edwards, J.C.S. Dalton, 1972, 2325.
W. Haase, Chem. Ber., 1973, 106,41.
L. Bernander and G. Olofsson, Acta Chem. Scand., 1973, 27, 1034.
9 2 5 Yu. Ya. Fialkov, Yu. A. Karapctyan, and V. P. Basov, Rum. J. Inorg. Chem., 1972,
17, 919.
8 2 8 D. M. Byler and D. F. Shriver, Inorg. Chem., 1973, 12, 1412.
9 a * M. Burgard and E. A. C. Lucken, J. Mol. Structure, 1972, 14, 397.
Q28 D. Beierl and A. Schmidt, Chern. Ber., 1973, 106, 1637.
Sa9 W. Buder and A. Schmidt, Chem. Ber., 1973, 106,2877.
Q22
923
Elements of Group V
551
and the oxygen (Sb-0 = 2.317
The Sb-0 distance in the tetrachloroethylene carbonate adduct is long (2.40A), in agreement with a relatively
small degree of interaction (low donor number) between the carbonate and
antimony p e n t a ~ h l o r i d e Reaction
.~~~
between the bis(methy1amide) of oxalic
acid and antimony pentachloride in 1 ,Zdichloroethane or chloroform solution
gives (146).932A single-crystal X-ray structure shows that the Sb-Cl dis-
tances fall between 2.301 and 2.355 A, but the C-N bonds are 1.274 and
1.495 A, in agreement with some degree of double-bond character for the
former, as shown.933A complex of pivaloyl chloride is formed when ButCl
and carbon monoxide react in sulphur dioxide containing antimony penta~ h l o r i d eThe
. ~ ~compound is considered to be present mainly as the polar coordination complex ButCOCI,SbCl5but with a small amount of the ion pair
ButCO+ SbCl;.
Thermal methods show that antimony(v) chloride forms compounds with
univalent metal chlorides which increase in thermal stability with the atomic
number of the
Phosphorus pentachloride similarly gives a stable
compound, but compounds from Ca, Sr, Ba, Ag, and SeIVchlorides are less
stable, and only eutectics are observed with Al, Ga, In, SbIII, and FeTI1
chlorides. In liquid sulphur dioxide, stoicheiometricamounts of KN,, KNCO,
and KCN react with antimony pentachloride to give, respectively, the salts
KSbCl,N,, KSbCl,NCO, and KSbCl,CN,936 and the compounds give i.r,
and Raman spectra that can be assigned on the basis of C,,symmetry for the
immediate environment of the antimony. On further reaction with SbC&
the azido- and cyanato-compounds give the neutral dimeric species (SbCI,N&
and (SbCl,NC0)2. Reactions with NaNO, and Na2C0237lead to evolution
of NOCl and CO,, respectively, and, although compounds such as
NaSbCI,NO, are possibly intermediates, the antimony is converted into
NaSbC1, together with Sb02Cl in the carbonate reaction.
The I&l+ and BrICl+ cations, which can be stabilized as the SbCl; salts,
result from direct combination of the appropriate halogen in the presence of
930
931
932
933
934
935
@36
03'
B. Chevrier, J.-M. Le Carpentier, and R. Weiss, Acta Cryst., 1972, B28,2667.

H. Kietaibl, H. Vollenkle, and A. Wittmann, Monatsh., 1972, 103, 1360.
W. Klein, D. Krauss, and H. P. Latscha, 2. anorg. Chem., 1973, 401, 85.
B. Kruss and M. L. Ziegler, 2. anorg. Chem., 1973, 401, 89.
M. Nojima, F. Shiba, M. Yashimura, and N. Tokura, Chem. Letters, 1972, 1133.
N. D. Chikanov, Russ. J. Inorg. Chem., 1972, 17, 1338.
U. Miiller, 2. anorg. Chem., 1973, 396, 187.
R. Hauft and A. Schmidt, 2.anorg. Chem., 1973,397,40.
552
aiitimony p e n t a ~ h l o r i d e .The
~ ~ ~salt [Cl,CNH :CCl,]+SbCl; results when
trichloromethyl isocyanide dichloride reacts with SbCl, in the presence of
hydrogen chloride.939On heating to 60 OC hydrogen chloride is eliminated,
giving a species considered to be [Cl,C:N:CCl,]+SbCI~ on the basis of
vibrational data.
In pyH+ SbCl;, the ClSbCl angles in the anion average 90' but the Sb-CI
distances range between 2.21 (2) and 2.44(2) A.g4oThe 4-methylpyridinium
nonabromoantimonate(v) structure shows the presence of SbBr; and Br;
ions.g41The former are slightly distorted octahedral with a mean Sb-Br
distance of 2.563 A while the latter are centrosymmetric (Br-Br = 2.551 A).
Almost linear chains are formed from the two ions with Br - - - Br contacts
of 3.444 A.
Bonds to Oxygen.-Thermodynamic data for SbO, (AG: = -80.69 and
AH: = -100.0 kcal mol-l) and Sb(OH), (AG," = -194.10 and AH," =
-236.6 kcal mol-l) have been calculated from solubility measurements of
Sb20, in sodium hydroxide solution.g42Oxidation of SblI1 by TllI1 in perchloric acid solution requires the two transition states [T10H,HSb0J2+ and
[TI,HSb0,]3+, but the former accounts for ca. 85% of the reaction.943A
tentative rate law is given and the energy and entropy of activation are
16.0 -4: 0.4 kcal mol-l and -13.1 f 1.8 cal K-l mol-l, respectively. The
formation of potassium antimony1 tartrate and contradictory evidence about
its properties have now been resolved.g44The complex, after drying over calcium chloride, is a monohydrate which loses water to give the anhydrous
compound above 160 OC and decomposes when heated above 265 OC. pH
titration and i.r. data point to (147) as the structure of the compound.
Too\
CHOAb
I
1
CHO
COO- K*
(147)
Electrical conductivity measurements when calcium oxide is added to

antimony oxide show a solutesolvent interaction at the ratio Ca0,20Sb,03
but the addition of magnesium oxide on the other hand has no effect.945
s38
939
940
941
942
943
B44
945
J. Shamir and M. Lustig, Inorg. Chem., 1973, 12, 1108.

A. Schmidt, Chem. Ber., 1972, 105, 3050.
S. K. Porter and R. A. Jacobson, Crysr. Struct. Comm., 1972,1,431.
S . L. Lawton, D. M. Hoh, R. C. Johnson, and A. S. Knisely, Inorg. Chem., 1973,12,
277.
V. P. Vasil'ev and V. I. Shorokhura, Russ. J. Inorg. Chem., 1973, 18, 161.
P. D. Sharma and Y. K. Gupta, J.C.S. Dalton, 1973, 789.
R. K. Iyer, S. G. Deshpande, and G. S. Rao, J . Inorg. Nuclear Chem., 1972,34,3351.
N. Zenaidi, R. Renaud, and F.-A. Josien, Compt. rend, 1973,276, C, 1297.
Elements of Group V
553
Data also show that it is possible to differentiate between antimonites
(Sb20$), antimonates (Sb20i-), and Sb,O:; species by their different effects
on the conductivity of antimony(II1) oxide. Vibrational data and n.q.r. and
mass spectral information are presented for compounds in the series Sb(OR),
and Sb(SR),.843
The formation of antimonic acids (HSbO,) in aqueous solution has been
followed by a number of techniques, including potentiometric tit ration^.^^^
Although the soluble a-form accounts for the bulk of the material in freshly
prepared solutions, there is a great tendency to form condensed species, and
crystallization gives the /?-form with a pyrochlore structure. Factors such as
acidity, ionic strength, and method of preparation influence the a+ fl
transformation, and evidence is presented for a further, strongly ionized,
y-form which is probably of an intermediate degree of condensation. Major
changes in the i.r. band at 630 cm-l take place when hydrated antimony(v)
oxide is progressively dehydrated, and bands at ca. 455 and 755 cm-l increase
in intensity as the degree of condensation of the Sb(0H); units increa~es.9~~
The data also indicate that adsorbed water together with terminal and
bridging hydroxy-groups are present in the crystalline material. Ion-exchange
reactions on crystalline antimonates have been
The structures of compounds with the composition AsS5+03,where
B = Sb, Bi, Nb, or Ta, have been considered in relation to the relative sizes,
Madelung energies, polarizability of the A cations, and covalence of the
B-0 bonds.949For antimony and bismuth, the latter factor inhibits the
formation of linear Sb-0-Sb
and Bi-0-Bi
bonds, while electrostatic
forces inhibit the formation of Sb-Sb or Bi-Bi pairs. The potassium antimonate obtained by crystallizing from water the product obtained by fusing
together antimony(v) oxide and potassium hydroxide is best represented as
KSb(OH)6,0.5H,0 according to chemical analysis and i.r. data.950Three
condensed antimonates, KSbO3,1.8H,O, K0.,SbO3,1 .8H,O, and Ko$b03,
1.3H20, have also been obtained, and changes in their i.r. spectra are consistent with the formation of a polymeric lattice of the pyrochlore type. On
heating to 700 ' C , Ca,Sb,O, (pyrochlore) is transformed into weberite, while
the corresponding lead pyrochlore is changed to a rhombohedrally distorted
p y r o c h l ~ r e The
. ~ ~ ~crystal chemistry of the 2-5 oxide pyrochlores and the
relationship between the phases are also discussed. lz1Sb and l19Sn Mossbauer
measurements show that antimony and tin are in the +5 and +4 oxidation
states, respectively, in the Sn,-,Sb,02 system.952
948
B47
948
g49
95O
961
952
J. Lemerle, Rev. Chim. minkrule, 1972, 9 , 863.

T. G. Balicheva and N. I. Roi, Izvest. Akad. Nauk. S.S.S.R., Neorg. Materialy, 1973,
9,277.
J.-P. Jolivet and J. Lefebvre, Rev. Chim. minerale, 1972, 9, 845.
J. B. Goodenough and J. A. Kafalas, J. Solid-state Chem., 1973, 6,493.
T. G. Balicheva and N. I. Roi, RMSS.
J . Inorg. Chem., 1972, 17, 1556.
F. Brisse, D. J. Steward, V. Seidl, and 0.Knop, Canad. J. Chem., 1972,50,3648.
T. Birchall, R. J. Bouchard, and R. D. Shannon, Canad. J. Chem., 1973,51,2077.
554
Pure VSb04 has been prepared and shown to have a structure similar to
rutile, with a random distribution of Sb and V atoms.953Magnetic measurements rule out the Sb111VV04formulation but it is not possible to make a
decision between the alternatives SbVV11104 and SbIVVIV04. The ferroelectric properties of synthetic SbNbO, prepared by a hydrothermal method
have been studied,954and a phase diagram for the Li(Ta,Sbl-,)03 system has
been constructed from X-ray data.955
A new series of alkali metal-rare earth antimonates has been prepared by
heating the alkali-metal carbonate, rare-earth oxide, and antimony(n1) oxide
in the ratio 1 :1 :4 to give non-stoicheiometric phases with the pyrochlore
structure.956The product with yttrium is represented by M5Y3Sbl,05,. A
number of mixed rare earth-antimony(n1) oxides 2Ln,03,xSb203,where x =
3.0-3.8,
have been prepared.g57 Further pyrochlore-type compounds
MSbWO,, where M = K, Rb, Cs, or T1, result when mixtures of W 0 3 ,
Sb203, and M2C03are heated in a current of oxygen,958and the species in
which M = H,O, NH,, or Ag can be prepared by ion exhange with the potassium or rubidium compounds.959
Bonds to Sulphur or Selenium.-Antimony(rI1) tris(dithi0carbamates) result
when reaction takes place between antimony(II1) chloride, carbon disulphide,
and arnine~.*~
Details for the preparation of SbSI have been given.960The
new ternary compound Na3SbS, has been observed in a study of the Na3Sb-S
and the primary crystallization
quasi-binary section of the Na-S-Sb
regions for NaSbS,, Na,SbS,, Na3SbS4,and Na,Sb,Sg have been defined.962
Compounds with compositions In2S3,3Sb2S3
and In,S3,Sb,S3 exist, according
to thermal and X-ray investigations in the binary system.963Bonding in the
mineral berthierite, FeSb,S4, is predominantly covalent, and the iron atoms
are found to be in the d6 high-spin state from magnetic susceptibility and
Mossbauer data.g64
Thermal investigation of the Tl,SeSb,Sq system shows evidence for the
compounds TI,SbSe, and T1SbSe,.965
H. Schuer and W. Klemm, 2.anorg. Chem., 1973,395,287.
V. I. Popolitov, A. N. Lobachev, V. F. Peskin, L. N . Syrkin, and N. N. Feoktistova,
955 V. I. Nesternenko and I. G. Ismailzade, Soviet Phys. Cryst., 1973, 18, 112.
D56 J.-M. Vinson and J.-P. Faurie, Compt. rend., 1973,276, C, 1183.
957 G . Adachi, M. Ishihara, and J. Shiokawa, J. Less-Common Metals, 1973, 32, 175.
958 C.Michel, D . Groult, and B. Raveau, Materials Research Bull., 1973, 8,201.
958 D . Groult, C. Michel, and B. Raveau, J . Znorg. Nuclear Chem., 1973, 35, 3095.
9 6 0 A. Rabenau and H. Rau, Inorg. Synth., 1973, 14, 161.
961 A. V. Salov, S. I. Berul, V. B. Lazarev, and A. S. Kanishcheva, Russ. J. Znorg. Chem.,
1972,17, 1758.
V. B. Lazarev, A. V. Salov, and S. I. Berul, Russ. J . Inorg. Chem., 1973, 18, 112.
n63 N. M. Kompanichenko, I. S. Chaus, V. D. Sukhenko, I. A. Sheka, and V. N. Lugin,
Russ. J. Inorg. Chem., 1973, 18, 569.
9 6 4 J. D. Donaldson, A. Kjekshus, A. D. Mukherjee, D. G. Nicholson, and J. T. Southern,
Actu Chem. Scand., 1972,26,4063.
s65 A. Graumann and P. Bohac, J. Less-Common Metals, 1973, 31, 314.
953
D54
Elements of Group V
555
5 Bismuth
General.-Liquid bismuth has been used as the solvent for calorimetry and
data for the enthalpy of solution of copper, indium, and tellurium have been
obtained.9G6
Enthalpy of formation data are also given for a series of copper
selenides. Studies on the distribution of lithium and bismuth between liquid
Li-Bi alloys and molten LiCl suggested that a salt-like species Li,Bi was
being selectively dissolved from the alloys.g67The mutual solubility of thorium
and the metallic lanthanides La, Nd, and Eu in bismuth over the range
350-700 "C shows evidence for the formation of solid compounds with the
composition ThLnBi,.968
Reduction of a 3:2 mixture of HfCl, and BiCl, with elemental bismuth
gives Bil,(HfCl6),, which from X-ray studies contains the Bii+ and Bi+ ions
in addition to distorted H f C l r ions.969The Bii+ has a tri-capped trigonalprismatic structure which is closer to full D,, symmetry than that in Bi6CI,,
and the Bi+ is trigonally co-ordinated to chlorine atoms. The chemistry of
bismuth, particularly in its lower and fractional oxidation states, is a basis for
predicting the chemical behaviour of element 115, but the lack of data in
bismuth systems hampers effective e x t r a p o l a t i ~ n . ~ ~ ~
The organometallicchemistry of bismuth has been reviewed.g71An electrondiffraction study of trimethylbi~muth~~~
leads to the following parameters: r(Bi-C) = 2.264(4); r(C-H) = 1.095(17) A; LCBiC = 96.7(1.0);
LBiCH = 107.6(1.O)". Tetraphenylbismuth nitrate and trichloroacetate can
be obtained from the chloride by metathesis, and unlike the latter are stable
for some hours at room ternperat~re.~',A five-co-ordinate structure rather
than an ionic bismuthonium structure is indicated for the conipounds from
i.r. and molecular weight data. In the corresponding perchlorate, however,
tetrahedral Ph,Bif cations [C-Bi = 2.18(2) A] and ClO, anions are
present.974 Further cationic bismuth(v) species with formulae such as
[(Ph,BiL),O]X, and [Ph,BiL2]X2 have been prepared for L = dimethyl sulphoxide, pyridine oxide, triphenylphosphine oxide, and triphenylarsine oxide
and X = CIO,, BF,, and PF,.975TheBi-0 stretching mode has been assigned
to a band between 430 and 350 cm-l. Attempts to prepare bismabenzene
(148) by allowing 1,4-dihydro-l ,l-dibutylstannabenzene (149) to react with
bismuth trichloride led to the separation of 1,4-dihydro-l-chlorobismabenzene
966
967
968
969
970
971
972
973
974
975
K. G . Skeoch and R. D. Heyding, Canad. J. Chem., 1973,51, 1235.

C. M. Ferris, M. A. Bredig, and F. J. Smith, J. Phys. Chem., 1973, 77, 2351.
F. J. Smith, J. Less-Common Metals, 1972, 29, 73.
R. M. Friedman and J. D. Corbett, Inorg. Chem., 1973, 12, 1134.
G. P. Smith and H . L. Davis, Inorg. Nuclear Chem. Letters, 1973, 9,991.
L. D. Freedman and G. 0. Doak, J. OrganometaIIic Chem., 1973, 48,292.
B. Beagley and K. T. McAloon, J . Mol. Structure, 1973, 17, 429.
R. E. Beaumont and R. G . Goel, Inorg. Nuclear Chem. Letters, 1972, 8, 989.
J. Bordner and L. D. Freedman, Phosphorus, 1973, 3, 33.
R. E. Beaumont, R. G. Goel, and H. S. Prasad, Inorg. Chem., 1973,12, 944.
556
(1 50).976 Dehydrochlorination gave only polymeric material but bismabenzene may have transient existence in the system.
Bonds to Halogens.-Two
lines with markedly different temperature coefficients are observed in the 35Cln.q.r. spectra of solid bismuth trichloride,
probably as a result of volume effects associated with different intermolecular
bonding.977The Raman spectra of the solid and molten trichloridesg3are
markedly different, and the latter is best interpreted in terms of the presence
of discrete molecules with C,, symmetry. Addition of varying amounts of
potassium or caesium chlorides gives BiCl; and BiCl:-, with C,, and 0,
symmetry, respectively, but AICl, ions are not produced when aluminium
chloride is added, and the melt consists of BiCl, and Al,Cl,.
Far-i.r. spectra of benzene solutions of chloro- and bromo-bismuth(1Ir)
anions,978ion-paired to tertiary or quaternary ammonium cations, indicate
that C,,symmetry is the highest possible for the Six; species, and the Six:compounds have square-pyramidal geometry (C,,); symmetry lower than
D,, is shown for species with Bi,X:- ions. In all cases examined here, the lone
pair showed stereochemical activity and there was no evidence for BiXE
monomeric species. The situation in aqueous HBr and HI solutions of bismuth(m) is different, and Raman spectra can be interpreted on the basis of
Six:- and BiX,(H,0)2- being the only ions of significance at respectively
high and lower X:Bi ratios.913 1.r. and Raman spectra for Six:-, where
X = GI, Br or I, and BiBri- have been measured and assigned, and some
force constants calculated.914
Stability constants for the bismuth(Ir1) iodide species BiI:-n, n = 1-6,
have been calculated from solubility
and thermodynamic data for
BiClE- can be obtained from heats of mixing of bismuth perchlorate and
hydrochloric acid.980
Bismuth trihalides along with the analogous arsenic and antimony compound form complexes with metal c a r b o n y l ~ ;with
* ~ ~ bismuth, however, only
neutral species such as CI,BiFe(CO),Cp and Bi [Co(CO),PPh,], were isolated.
The four bands observed in the i.r. spectra of BiOCl, BiOBr, and BiBI in
the range 40-600 cm-l are in agreement with predictions based on the DIh
976
977
978
97g
B80
A. J. Ashe tert., and M. D. Gordon, J . Amer. Chem. SOC.,1972, 94, 7596.

G. C. Gillies and R. J. C. Brown, Canad. J. Chem., 1973, 51, 2290.
B. A. Work tert., and M. L. Good, Spectrochim. Acta, 1973, 29A, 1547.
V. A. Fedorov, T. N. Kalosh, L. I. Shmydko, and V. E. Mironov, Russ. J. Znorg.
Chem., 1972,17,1086.
V. P. Vasilev and A. A. Ikonnikov, Russ. J . Inorg. Chem., 1972, 17, 1700.
Elements of Group V
557
space
Only in the case of BiOBr are the expected six Raman bands
observed; assignments are proposed.
D.t.a. data show that BiCl,,GaCl, (m.p. 162 "C) is formed from the components, but there is no appreciable solubility in the BiCI, systems with
magnesium, calcium, strontium, barium, or cadmium chlorides, and the
systems with HgCl,, AgCl, and Hg2Clzshow simple e u t e c t i ~ sThe
. ~ ~equilib~
rium LiBiCl,-KBiCl, diagram shows the formation of the congruently
melting species 7LiBiC1,,3NaBiCI,.983
The Raman spectrum of a solution of BiF, in hydrogen fluoride shows lines
due to the pentafluoride only, indicating that it is a weaker Lewis acid than
SbF,,984but on addition of caesium fluoride, CsBiF, could be obtained as a
solvate with 2-3 moles of HF. The Raman spectrum was assigned on the
basis of octahedral symmetry.
Bonds to Oxygen.-A high-temperature mass spectrometric study of the
vaporization of bismuth(r1r) oxide985shows that the process can be best
represented by the equation: Bi,O,(g) -+Bi(g) 02(g) Bi,O,(g), where
n = 1 - 4 . The temperatures at which the various forms of Bi,O, interconvert
have been investigated and the transition from cf to S is found to occur at
731 'Cgs6
The hydrolysis of bismuth(1rr) and the precipitation of Bi(OH), have been
studied over a wide pM range by tyndallometric methods and high-voltage
electrophore~is,~~~
and the conditions under which cationic perchloratocomplexes, hydroxo-complexes, and highly polymerized bismuth species
exist are designated. The reduction of bismuth(rI1) in acid perchlorate involves
the BiOH2+species in the slow stage, according to polarographic measurem e n t ~ The
. ~ ~kinetics
~
of formation and dissociation of the bismuthyl complex Bi,(OH)ii have been investigated using pressure-jump and stopped-flow
techniques, and a rate law is givengs9Oxidation of bismuth in the presence
of hydrogen peroxide, nitric acid, and oxygen has been studied, and oneproduct isolated is formulated as [Bi,06(OH),](N03)4,2H20.990
On the basis of
this work the basic nitrate, which is usually given as BiONO,,BiOOH, is
better formulated as containing a polymeric cation, i.e. as [Bi,O,(OH),](N03)3,1.5HzO.
J. E. D. Davies, J . Inorg. Nuclear Chem., 1973, 35, 1531.

N. D. Chikanov and V. A. Ugai, Russ. J . Znorg. Chem., 1973, 18,446.
@a3 N. I. Kaloev and A. K. Tebiev, Russ. J. Inorg. Chem., 1973,18,448.
T. Surles, L. A. Quarterman, and H. H. Hyman, J. Inorg. Nuclear Chem., 1973, 35,
670.
985 E. K. Kazenas, D. M. Chizhikov, Yu. V. Tsvetkov, and M. V. Ol'shevskii, Doklady
Chem., 1972,207,867.
986 R. Matsuzaki, A. Sofue, and Y. Saeki, Nippon Kaguku Kaishi, 1973,491.
987 B. PokriC and Z. PuEar, J. Inorg. Nuclear Chem., 1973,35,3287.
C. Dragulescu, A. Nimara, 1. Julean, and D. Marandiuc, Rev. Roumaine Chim., 1973,
18, 583.
V. Frei, G. Mages, and H. Wendt, Ber. Bunsengesellschaft phys. Chem., 1973,77,243.
sgO B. S. BrEiE, D. Kolar, F. Lazarini, and M. MaleSiE, Monutsh., 1973, 104, 365.
s81

558
Stability constants have been determined spectrophotometrically for the
monoprotonated and normal complexes of bismuth(rI1) with edta and diaminocyclohexanetetra-acetic acid.gg1 Treatment of BiCI, with C1,O in
phosphoryl chloride leads to a dichlorophosphate Bi(PO,CI,),POCI,, in
which the bismuth atom is co-ordinated by oxygen from both the P0,C12
group behaving as a bidentate ligand and from the POCI, solvate molecule.g92
Bismuth triarenesulphinates Bi(O,SR), can be synthesized successfully by
allowing the triacetate to react with an arenesulphinic acid in glacial acetic
acid.993The spectra indicate bridging 0-sulphinate co-ordination to give
polymeric species, and the compounds on heating lose sulphur dioxide to give
the corresponding triarylbismuth. An excess of boiling trifluoroacetic anhydride converts Bi203 and NaBiO, into Bi(CF,CO2), and NaBi(CF,CO,),,
respectively.994
X-Ray crystallographic investigation of the Bi,O,-TeO, system at 450 "C
has shown that the new phases BiloTe,Olg and Bi2Te4011exist.995
Kinetic data point to the rate of oxidation of I-, Br-, C1-, SCN-, and T1+
by bismuth(v) in perchloric acid solution as depending only on the concentration of bismuth;996the energy of activation and entropy change are 7.1 rt
0.3 kJ mol-l and -187 J Kel mol-l, respectively. The bismuth(v) solutions
were found to be considerably more stable than expected, and could be kept
for ca. five days without significant decomposition. A value of 2.03 f 0.17 V
was obtained for the BiVIBilI1 half-cell reaction at 25 "C and [H+] = 0.5
mol 1-1 and I = 2.0 moll-l.
The compound Na,BiO, prepared from sodium peroxide and bismuth trioxide has a structure based on a variant of the NaCl structure, with chains of
the formula $[Bi04,2+2,1].gg7
The Madelung part of the lattice energy has
been calculated for this and other possible structures. From i.r. spectroscopy
in the Bi-0 region, the charge distribution in the perovskite BaBiO, is
such that the bismuth atoms are equivalent, and the compound is considered
to contain Bi4f.99s A series of new bismuth cadmium pyrochlores
CdLzBiz(Ta,,l,Cd,l,)O,,
with 0 < x Q 1.6, has been synthesized,999and a
definite compound Bi,CuO4 has been obtained in a study of the CuO-Bi,O,
system above 500 oC.looo
Bonds to Sulphur or Selenium.-The crystal structure of Bi,In4S,, recently

synthesized by vapour-transport reactions with iodine, indicates that three
of the indium atoms are octahedrally co-ordinated by sulphur while the fourth
ggl
gga
993
gg4
9g5
9g6
gg7
998
looo
B. P. Karadakov and K. R. Ivanova, Zhur. analit. Khim., 1973,28,525.

A. Klopsch and K. Dehnicke, 2. Naturforsch., 1972, 27b, 1304.
G. B. Deacon and G. D. Fallon, Austral. J. Chem., 1972,25,2107.
P. V. Radheshwar, R. Dev, and G. H. Cady, J. Inorg. Nuclear Chem., 1972,343913.
B. Frit and M. Jaymes, Rev. Chim. minkrale, 1972, 9, 837.
M. H. Ford-Smith and J. J. Habeeb, J.C.S. Dalton, 1973, 461.
B. Schwedes and R. Hoppe, 2.anorg. Chem., 1972, 393, 136.
J. T. W. de Hair and G. Biasse, Solid State Comm.,1973, 12, 727.
G. Desgardin, G. Jeanne, and B. Raveau, Compt. rend., 1973, 276, C, 851.
J . 4 . Boivan, D. Thomas, and G. Tridot, Compt. rend., 1973,276, C, 1105.
Elements of Group V
559
is in tetrahedral co-ordination.lool The two bismuth atoms show strong coordination to five sulphur atoms but for one there is a sixth sulphur which is
only weakly bonded and for the second, two further sulphur atoms contribute
to the co-ordination polyhedron. The nickel atoms in parkerite, Ni,Bi,S,,
occupy two non-equivalent positions and are octahedrally co-ordinated
to four bismuth and two sulphur atoms.loo2The structure of the rare bismuth
sulphide mineral nuffieldite, Pb2Cu(Pb, Bi)Bi,S,, is dominated by a quadruple PbBiS, chain,103 identical to that found in PbCuBiS,, in which the
heavy metals are co-ordinated by five sulphur atoms.
A new modification of bismuth(II1) selenide, Bi,Se, (11), is obtained at high
temperature and pressure and is isostructural with Sb2S,;lW4the Bi-Se
distances in the chains which make up the structure vary between 2.82 and
2.85 A. Heating a mixture of bismuth, the trioxide, and selenium to ca.
800 "C in a quartz tube gives Bi202Se,which from X-ray powder data has a
(Na,,25Bi0t
. ,5)202Cltype struct ure.loo5
lool
G. Chapuis, Ch. Gnehm, and V. KrBmer, Acta Cryst., 1972, B28,3128.
looaM. E. Fleet, Arner. Mineralogist., 1973, 58, 435.

loo3I. Kohatsu and B. J. Wuensch, Z . Krist., 1973, 138,
loo4
343.
E. Ya. Atabaeva, S. A. Mashkov, and S. P. Popova, Soviet Phys. Cryst., 1973, 18,
104.
H. Boller, Monatsh., 1973, 104, 916.
loo6
Elements of Group VI
~
BY M. G. BARKER
1 Oxygen
The Element.-A coulometric analyser for oxygen has been describedl based
on the use of a porous catalytic silver electrode, where the active surface area
is controlled by the application of a pressure difference across the cell.
Oxygen concentrations over the range l00-0.007% can be measured. The
saturation concentration of oxygen dissolved in liquid sodium has been
measured2 by an e.m.f. method using a thoria-yttria electrolyte. The separation of 150in the 7-activation determination of oxygen in selenium has
been carried out3 by fusion of the sample under an argon atmosphere containing sulphur vapour. The sulphur dioxide formed was trapped in hydrogen
peroxide for activity measurements. The detection limit found for the
technique, which may also be used for the dztermination of nitrogen in
selenium, was 0.05 pg oxygen (g selenium)-l.
Single-crystal neutron diffraction data have been used4 to refine the crystal
structure of the paramagnetic ?-phase of oxygen at 46 K. Two of the eight
molecules in the Pm3m unit cell are randomly orientated along the 111 axes
at the 2(a) position and the remaining six molecules at the 6(d)position. The
observed data are in good agreement with theoretical calculations based upon
the usual MO model with two unpaired electrons in the p-rr antibonding
levels. The gas-phase e.s.r. spectrum of vibrationally excited molecular
oxygen has been obtained5 using a discharge sampling technique. The e.s.r.
signal of molecular oxygen, in several matrices at temperatures below 10 K,
has been found6 to be greatly influenced by the immediate molecular environment. The autoionization and photoelectron spectra of oxygen have been
recorded' between 800 and 850 A. High-resolution rotational analysis of the
J. Tenygl and B. Fleet, CoZZ. Czech. Chem. Comm., 1973,38, 1714.
H. U. Borgstedt, A. Marin, Z . Peric, and G. Wittig, Atomwirt. Atomtech., 1972, 17,
361.
J. Gosset and Ch. Engelmann, Radiochem. Radioanalyt. Letters, 1973, 13, 39.
D. E. Cox, E. J. Samuelson, and K. H. Beckurts, Phys. Rev. (B), 1973, 7, 3102.
T. J. Cook, B. R. Zegarski, W. H. Breckenridge, and T. A. Miller, J. Chem. Phys.,
1973,58, 1548.
H. Kon, J . Amet. Chem. SOC.,1973, 95, 1045.
J. A. Kinsinger and J. W. Taylor, Internat. J. Mass Spectrometry Ion Phys., 1973, 11,
461.
560
561
oxygen absorption spectrum in the region from 1085to 1170 A has been carried
out* for the first time. The magnetic susceptibility of solid oxygen-argon
mixtures has been obtainedg as a function of the temperature from 12 K to
the melting point. In the case of the 95 % o,-s % Ar system, the behaviour of
the magnetic susceptibility was similar to that of pure oxygen except for some
dynamical effects caused by the addition of argon to the oxygen lattices. In
the composition range between 92 % and 66 % O,, the appearance of a novel
phase, S, was observed from the magnetic susceptibility measurements.
An i.r. and vibrational analysis of the products formed from the simultaneous deposition of oxygen molecules and caesium atoms, at high dilution
in argon, has been carried out.1 Absorbances at 1115, 268, and 236 cm-l
were assigned to the v l , v3, and v2 modes, respectively, of the species Cs+Or.
The use of isotopic mixtures confirmed the assignments and also the isosceles
triangle configuration of Cs+Oz. The most intense mode of CszO was also
observed at 357cm-l, and a strong band at 1002cm-l showed isotopic
splittings for a species containing two oxygen molecules, which was assigned
to the caesium di-superoxide species CssOr. A Raman studyll of the same
system, and of the rubidium-oxygen system in argon at 15 K, has shown
signals arising from both the M+O, and M+O, species. Bands at 1110 and
1114 cm-l were assigned to intraionic 0-0 modes in Rb+OF and C s + 0 ~ ,
respectively; whereas bands at 298 and 287 cm-l were assigned to the intermolecular (02-02)modes in Rb+O; and Cs+O;i-,respectively. When tin
vapour is co-condensed, at 20 K, with krypton or nitrogen matrices containing
a few mole % of oxygen, the molecular species SnO, and Sn,O, were found12
to be the major reaction products. Small amounts of 0,, SnO, Sn30,, and
other tin-oxygen species were also produced. Normal-co-ordinate analysis
indicated that molecular SnO, is linear (Dmh),being formed by the direct
insertion of a tin atom into an oxygen molecule. The positive ionic products
resulting from the reaction of an oxygen molecular beam with metal-atom
beams of aluminium and barium have been studied.13 For the reaction of
barium and oxygen, the positive ions from the following three ionic processes
were observed.
(1) Associative ionization
Ba
+ Oz
+ e-
Ba
-+ BaO+
BaO:
(2) Reactive ionization

0 2
(3) Electron-transfer ionization

Ba
Oz -+ Bat
8
9
10
11
12
13
+ 0-
+ 0;
H. C. Chang and M. Ogawa, J. Mol. Spectroscopy, 1972, 44,405.

Y . Mori, A. Sakakibara, and H. Inokuchi, Bull. Chem. Sac. Japan, 1973, 46, 2305.
L. Andrew, J.-T. Hwang, and C. Trindle, J. Phys. Chem., 1973, 77, 1065.
R. R. Smardzewski and L. Andrews, J. Phys. Chem., 1973, 77,801.
A. Bos and J. S. Ogden, J. Phys. Chem., 1973, 77,1513.
R. B. Cohen, C. E. Young, and S. Wexler, Chern. Phys. Letters, 1973, 19,99.

For the reaction of aluminium with oxygen , only electron-transfer ionization
was observed:
562
A1
+ 0,
Al+
+ 0;
The ions AlO+ and AlOg were not detected. An n.m.r. study1* of thallium(1 +)
in aqueous solutions containing dissolved oxygen has indicated the possible
formation of a weak complex between the thallium and molecular oxygen.
Molecular oxygen reacts15with a high concentration of SO2 ions on magnesium
oxide to form stable SO3 radicals. E.s.r. spectra suggest sp hybridization on
the sulphur atom, with an oxygen-sulphur-oxygen bond angle of 112'. The
retention of molecular oxygen by certain alkaline-earth apatites [prepared by
the action of H202on ~-Ca,(PO,),] has been studied16by e.s.r. techniques.
Molecular oxygen was found to be present as the oxygen molecule, together
with the 0 2 ion and an unidentified oxygen radical.
Mass spectrometric studies1' of the adiabatic expansion of hydrogenoxygen and hydrogen-oxygen-nitrogen gas mixtures have revealed the formation of the HiO, species. This species is believed to be a relatively weakly
bound isomer which is less stable than hydrogen peroxide.
A @switched ruby laser has been used to measurela spectroscopically the
lifetime of singlet molecular oxygen in solution. The nature of the solvent was
found to have a remarkable effect on the lifetime of the species, with values
ranging from 2 ps in water to 700 ps in carbon tetrachloride. The production
of O(lS> in the photodissociation of CO,, 03,O,, and N20 has been investigatedlg at the 1216 k Lyman M. line. Relative quantum yields at this wavelength have been determined. The reaction of atomic oxygen with hydrogen
bromide has been studied20 by monitoring the e.s.r. spectra of O(3P2),
Br(2P3,2),OH(21;I,/,), and H(2S,,,> at various reaction times. The experimental results were found to be in accord with the mechanism:
+ HBr OH + Br
OH + HBr --+ H,O + Br
0
+ HBr
---+
Ha
+ Br
Ozone. The Raman spectrum of matrix-isolated ozone has been obtained21

from argon-oxygen mixtures deposited on a nickel-plated copper substrate at
l4
M. Bacon and L. W. Reeves, J. Amer. Chem. SOC.,1973, 95, 272.
l5
Y.B. Taarit and J. H. Lunsford, J. Phys. Chem., 1973,77, 1365.
l6
J.-C. Gourdon, C. Rey, C. Chachaty, J. C. Trombe, and J. Pescia, Compt. rend.,
1973,276, C,559.
J. W. Hastie, Chem. Phys. Letters, 1972, 17, 195.
la P. B. Merkel and D. R. Kearns, J. Amer. Chem. SOC.,1972,94,7244.
lS B. A. Ridley, R. Atkinson, and K. H. Welge, J. Chem. Phys., 1973,58, 3878.
2 o G.A. Takacs and G. P. Glass, J. PAYS.Chem., 1973, 77, 1182.
41 A. G.Hopkins and C. W. Brown, J. Chem. Phys., 1973, 58, 1776.
l7
563
20 K, after passing through a microwave discharge. In the matrix environment the two Raman bands due to the symmetric vibrations v1 and v2 are
polarized, whereas the antisymmetric stretching vibration v3 is depolarized.
The Raman spectra of argon-matrix, isolated ozone, and ls0-enriched
ozones have been measured.,, Assignments were v1 at 1104 cm-1 (very
strong), v2 at 701 cm-l (strong), and v3 at 1038 cm-l (weak). A valence angle
of 116.3' was calculated from four isotopic u3 assignments, which is in
excellent agreement with microwave values. The general quartic force field
for ozone has been determined23using the vibrational energy levels observed
for liquid ozone dissolved in liquid argon at 85 K, and with the vibrationalrot ational interaction constants determined from microwave measurements
The upper-state rotational constants for the (vl Y,
vg) combination band
of ozone have been analysed2*from high-resolution (0.07 cm-l) spectra. A
model has been presented25for the prediction of the shapes and energetics
of the low-lying electronic states of small polyatomic molecules such as ozone.
Molecules are considered which have one or two central atoms and which
involve co-ordination numbers of two or three. The model, which may be
used to predict bond angles to a good degree of accuracy, has been applied to
the following molecules of interest in Group VI; OF,, OCI,, H20z, Cloy,
S,O, ClO,, SH,, N,S,, NSF, ONF, N,O,, HNCS, HNCO, ozocyanate, and
thiocyanate. The total energy of the symmetrical, bent, ozone molecule, has
been studied26as a function of internuclear angle and distance. Ab initio MO
calculations were used to show a possible low-energy path, via a cyclic form,
for the thermal decomposition of ozone. The kinetics of ozone formation in
pulse radiolysis of oxygen gas at pressures from 7 to 400 kN m-2 have been
studied2' by optical absorption methods in the range 250-330nm. The
absorption spectra at different times, and the time dependence of the absorption at 250, 270, and 310nm, were interpreted in terms of three kinetically
distinguishable consecutive reactions. A further study2* of the kinetics of
ozone formation used the pulse radiolysis of oxygen-C,H, mixtures. Competition studies, in the absence and presence of sulphur hexafluoride, show
that C,H, depresses the primary yield of oxygen atoms from pulse-irradiated
oxygen. The maximum depression obtained by C2H4 was found to be the
same as that found for SFB.
A comparison has been made29between the i.r. spectra of (i) liquid ozone
synthesized from the glow-discharge plasma in oxygen, (ii) the peroxyradical condensate obtained from ozone by bombardment with atomic
hydrogen, and (iii) the calculated spectrum of 0,.The agreement found
+ +
a3
a4
a6
26
L. Andrews and R. C. Spiker, J. Phys. Chem., 1972, 76, 3208.

D. F. Smith, Spectrochim. Acta, 1973,29A, 1517.
D.E. Snider and J. H. Shaw, J. Mol. Spectroscopy, 1972,44,400.
G.W. Schnuelle and R. G. Pan, J . Amer. Chem. SOC.,1972,94,8974.
J. S. Wright, Carzad. J. Chem., 1973,51, 139.
P. L. T. Bevan and G. R. A. Johnson, J.C.S. Faraday I, 1973,69,216.
P. L. T.Bevan and G. R. A. Johnson, J.C.S. Faraday I, 1973,69,922.
L. I. Nekrasov and T. V. Yogodovskaya, Russ. J. Phys. Chem., 1972,46,1547.
37
564
between the majority of the experimental and theoretical frequencies suggests

that the O4 molecules, formed together with ozone in the low-temperature
condensation of the oxygen plasma, are present in liquid ozone. The interaction of ozone with semiconducting inorganic and organic solids has been
examined.3O Evidence is presented that a charge-transfer complex is formed of
the type OF-solid+. Electrical measurements support the view that the formation of the complex is by a transfer of a valence-bond electron of the solid
to the adsorbed species. The i.r. spectrum31 of the product formed by the
codeposition at 15 K of alkali-metal atoms and ozone showed very intense
bands near 800 cm-l and weak bands near 600 cm-l. The bands showed the
appropriate oxygen isotopic shifts for assignment to the v3 and vz modes of
the ozonide ion. Energetic considerations clearly indicated bonding of the
metal cation to the ozonide ion. Further, it was found that the metal cation
was symmetrically bound to the ozonide ion in a C,, symmetry. The symmetrical interionic stretching mode for Cs+Or was found to occur at 281 crn-l.
of mixtures of alkali-metal atoms
Argon and krypton laser Raman
and ozone molecules in an argon matrix showed very intense bands, shifted
1010 cm-l below the exciting lines, which could be assigned to the 0-0mode
of the 0
: ion. A photochemical study3, of the reaction between ozone and
the compounds CS, and COS has shown that the products of the 0,-CS2
reaction are COS, SO,, and SO,, with carbon monoxide being produced in
minor amounts. Carbon dioxide, carbon monoxide, sulphur trioxide, and
sulphur dioxide are the products of the ozone-COS reaction. It is suggested
that the primary products in the reaction with CS2are COS S and S,
CO; while with COS the primary products are C 0 2 S and CO SO. No
evidence was found for species such as CS,O or C02S, analogous to CO,,
which is produced in the addition of O(lD) to CO,. The gas-phase reaction of
ozone with CCl,CH2 at 25 OC has been studied%by monitoring the consumption of ozone by U.V. and that of the product and olefin by i.r. methods. The
observed products of reaction were CCl,O, HC02H, CH,ClCCl(O), COYO,,
HCl, and presumably water. In the absence of oxygen the ratio CC12CH2:0,
approaches 2 but the quantity of CCl2Oproduced per mole of ozone consumed
is between 0.25 and 0.4 mol. With an excess of oxygen the latter ratio becomes
unity, but the ratio of CCl,CH, to ozone consumed approaches 5. The rates
of reaction of ozone dissolved in water with SO,, NO2, and H2S have been
mea~ured.3~
A study by Raman spectro~copy~~
of the condensed products
from electrically dissociated water vapour and other related systems has
revealed the presence, not only of ozone in appreciable amounts, but also of
30
32
33
34
35
36
H. Kiess and T. Freund, J. Phys. Chem., 1973,77, 556.

R. C. Spiker and L. Andrews, J. Chem. Phys., 1973,59, 1851.
L. Andrews and R. C. Spiker, J . Chem. Phys., 1973, 59, 1863.
P. R. Jones and H. Taube, J . Phys. Chem., 1973,77, 1007.
L. A. Hull, I. C. Hisatsune, and J. Heicklem, Canad. J. Chem., 1973, 51, 1504.
S. A. Penkett, Nature Phys. Sci., 1972,240, 105.
I . L. Arnau and P. A. Gigutre, Canad. J . Chem., 1973, 51,1525.
565
molecular oxygen in still greater amounts, trapped at 80K. The concentration of ozme relative to the hydrogen oxides varied with experimental
conditions, as did the concentration of trapped oxygen. On warming up under
vacuum the intensity of the oxygen and ozone bands began to decrease even
before the crystallization temperature was reached (-150 IS),thereby confirming that the gas evolution at that stage is merely a desorption process. The
often quoted ratio of total evolved oxygen to residual hydrogen peroxide could
not, therefore, be a reliable index of the formation of the hydrogen polyoxides
H203and H,04 in these systems. The fundamental vibrations of the ozone
molecule, v1 = 1106, v2 = 703, and v3 = 1036 cm-l, were confirmed by
polarization and isotope-shift measurements.
Ion Species.-An attempt has been made3 to use the heats of formation of
oxygen-containing inorganic and organometallic compounds in the vapour
state, and of certain solid compounds with co-ordinate bonds, to estimate the
energy associated with the oxygen-element bond. The system of energetic
increments (conventional bond energies) allowed some qualitative conclusions to be drawn about the ratio of the energies of single and multiple
bonds between oxygen and various elements. The calculated radii of the ions
02-and S2- have been derived3*from a study of the calculated radial distributions of electrons in ionic crystals, metal oxides (NiO, FeO, MgQ), and
metals (Li, Na, K). Formulae which may be used to calculate the energies of
hybridized valence states, involving s-p hybrid orbitals, have been given,39
together with the prescriptions and numerical data for the actual evaluation of
the hybridized valence-state energies of the atoms and ions of oxygen. The ion
Og+ has been observed40in a mass-spectrometric study of natural molecular
oxygen. The ion was observed only with difficulty since the species l60:+,
which comprises 99.5% of the total, has the same mass/charge ratio as the
monatomic, singly charged ion lSO+. Even the ion (1s0180)2+,
comprising
0.4 % of the total, is obscured by the OH+ ion from the trace of water always
present in the spectrometer. The only ion which could be detected was therefore 1601702$-,
which comprises only 0.08 % of naturally occurring Oi+. A
high-resolution electron time-of-flight spectrometer has been used41 in a
transmission experiment to study resonances in electron-oxygen scattering,
corresponding to vibrationally excited levels of the 0 2 ion ground state. A
doublet structure due to spin-orbit coupling was observed. The unpaired
electron in the ozonide ion 03 is expected to occupy an antibonding MO,
but published experimental results indicate a shorter bond length and larger
force constants than in neutral ozone. MO calculations using the CNDO
approximation have been reported42for the ozonide ion and related species
37
38
39
*O
41
R. B. Dobrotin, Russ. J. Inorg. Chem., 1972, 17, 615.

V. P. Tsvetkov and L. V. Shevtsov, Metallojizika, 1972, 42, 42.
T. Anno, Theor. Chim. Acfa, 1973, 30, 129.
S. Meyerson and P. J. Ihrig, Internat. J. Mass Spectrometry Ion Phys., 1973, 10, 497.
J. E. Land and W. Raith, Phys. Rev. Letters, 1973,30, 193.
J. M. Sichel, Canad. J. Chem., 1973, 51, 2124.
566
(03,
SO,, SOT, O a , OF,) using both the CND0/2 and CNDO/BW methods.
Both methods predict that the bond lengths in 0: are 0.04 A longer than in
the ozone molecule, which is in agreement with qualitative MO theory, and
that the bond angle is one degree less than in the neutral molecule. The
CNDO/BW method predicts that the electron affinity of ozone is higher than
that of the oxygen atom, in agreement with experimental values, since a
stabilizing exchange effect outweighs the antibonding nature of the orbital
occupied by the extra electron.
Raman spectra of the polycrystalline alkali-metal superoxidesand ozonides
NaO,, KO,, RbOz, CsO,, KO,, and CsO, have been measureda at temperatures between 75 and 300 K. Solid-solid phase-transition effects were noted in
all the superoxides apart from CsO,. The spectra of the ozonides KO3 and
CsO, exhibited a single band at -1010 cm-l, which was assigned to the symmetrical stretching mode of the 0 3 ion. The vibrational structure of the
ground state and the electronic structure of the excited state for the ions O r ,
Sz,Sez, and SeS- dissolved in alkali-metal halide crystals have been studiedu
by means of emission measurements.
The nature of the centres formed on the surface of metallic oxides in the
presence of oxygen has been discus~ed,4~
and the various possible species OF,
03, 0;-,
0:-,Og-, and 0;-have been considered. E.s.r. data for some
centres which are generally described as being the ion 0-have been interpreted in terms of the hole centre Ot-,which is thought to be chemically more
reasonable. Oxygen enriched with 1 7 0 has been used46 to investigate the
nature of oxygen species adsorbed on some oxides using e.s.r. techniques.
Variations in the hyperfine constants for the ion 0 2 are thought to be due to
there being two different adsorption sites on MgO and ZnO, and it is thought
that in the case of supported molybdenum the 0 2 ion is adsorbed at an angle
to the surface. The metastability of oxygen paramagnetic centres adsorbed on
metallic oxides has been pointed out in a studyq7of the oxides TiO, and SnO,.
The species formed on the surface of zinc oxide, following the desorption of
oxygen, have been identified48as the ions OF at 180-190 O C and 0-at 285295 "C by e.s.r. A study of oxygen enriched with 1 7 0 2 adsorbed on slightly
reduced CeO,/SiO, catalysts has shown49that the spectra are consistent with
the adsorbed species being the 0 2 ion.
A general account of the modern views on the nature of inorganic peroxycompounds has been given.50The molecular oxygen anions Og-, OF,and 0 3
are considered together with the structures of simple peroxy compounds,
J. B. Bates, M. H. Brookes, and G. E. Boyd, Chem. Phys. Letters, 1972, 16, 391.
u M. Ikezawa and J. Rolfe, J. Chem. Phys., 1973,58,2024.
O5 M . C. R. Symons, J . Phys. Chem., 1972,76, 3095.
46 M. Che and A. J. Tenca, Chem. Phys. Letters, 1973,18, 199.
47 C. Hauser, Chem. Phys. Letters, 1973, 18, 205.
48 K. Tanaka and G. Blyholder, J. Phys. Chem., 1972,76, 3184.
48 M. Che, J. F. J. Kibblenhite, A. J. Tench, M. Dufaux, and C. Naccache, J.C.S.
Faraday I, 1973, 69, 857.
I. I. Volnov, Russ. Chem. Rev., 1972, 314.
43
567
peroxides, superoxides, and ozonides. Studies of the structures of complex
peroxy-compounds are briefly summarized, and the nomenclature of organic
peroxy-compounds is critically discussed, a new scheme of nomenclature
being proposed. The review contains 93 references in the bibliography. E.s.r.
measurements utilizing 1 7 0 have been carried
in order to test the proposition that the two oxygen atoms are not equivalent for the superoxide ion
formed by the transfer of one electron from a solid surface (a decationated
zeolite) to molecular oxygen. The observed hyperfine structure confirmed
that the two oxygen atoms are unequal and it was consistent with a peroxytype structure. A normal-co-ordinate analysiss2 of the dimethyl peroxides
CH300CH3 and CD,00CD3 has shown the oxygen-oxygen stretching
motion to be highly coupled for both molecules. Because of this, the 0-0
stretching frequency cannot be considered to be a reliable measure of the
oxygen-oxygen bond strength. In order to isolate the elementary reactions
responsible for the decomposition of hydrogen peroxide by iodine and its
compounds, the reactions at 50 OC of acid solutions containing 12, I-, HI0
etc. with hydrogen peroxide have been studied.53The concentration of I- and
I, was controlled by the use of TII(s) and 12(s). The rates of evolution of
oxygen, of consumption of H,02, and of production of H+ were measured,
and the following complex mechanism was proposed:
+ Ha02 + H I 0 + HZ0 + Op
+ HBOa + HI02 + H+ + Ha0
HI0 + HpOI + H+ + I- + HI0 + 0 2
HI02 + H+ + I2HI0
H201+ + H I 0 + H+
H I 0 + H2O
I- + H+ + Hp0a
I2 + H 2 0 + H I 0 + H+ + IHI02
H2OI+
--f
Oxygen Fluorides.-Non-empirical
SCF calculations have been carried O U

for the electronic ground state of oxygen difluoride, OF,. In general, the
agreement between experiment and calculation is quite good for many of the
molecular properties studied. CNDO/2 methods have been used55to calculate
the total energies of the 0,F2 and S2F2molecules. The oxygen-fluorine reaction, in a silent electric discharge using a circulating system, has been
studied56under various conditions. The reaction yields oxygen fluorides with
oxygen/fluorineratios from 1.1 to 2.04. At high temperatures the formation of
a compound with a composition close to 04F2increases. This is probably due
61
Y.B. Taarit and J. H. Lumsford, J. Phys. Chem., 1973, 77, 780.
62
M. E. Butwill-Bell and J. Laane, Spectrochim. A d a , 1972, 28A, 2239.

I. Matsuzaki, R. Sirnic, and H. A. Liebhafsky, Bull. Chem. SOC.Japan, 1972, 45, 3367.
S. Rothenberg and H. F. Schaefer, J . Amer. Chem. SOC.,1973, 95, 2095.
C. Leibovici, J. Mol. Structure, 1973, 16, 158.
I. V. Nikitin, A. V. Dudin, and V. Ya. Rosolovskii, Izvest. Akad. Nauk S.S.S.R.,Ser.
khim., 1973,269.
63
64
66

568
to the different thermal stabilities of 02F2and O,F, with the latter being more
stable at higher temperatures. New preparations of the violet and blue compounds of chlorine, fluorine, and oxygen have been reported.57The violet
compound was prepared by a 10 minute photolysis of a mixture of ClF, and
2 atm oxygen at 195 K and also by condensing CIF into a still containing a
liquid 0 4 F 2solution and photolysing the mixture. The blue compound was
prepared by the reaction of ClF, in excess, with 02F2at 119 K and also by the
removal of oxygen under vacuum from a solution of the violet compound in
ClF3. The most likely structure of the violet compound is thought to be
F2CI02F,as opposed to FOCIFOF, since decomposition of the violet compound produces 0,F2 and ClF. The production of the blue compound, by
removal of oxygen from a solution of the violet compound in CIF,, indicates
that an equilibrium exists between the two compounds which is sensitive to
oxygen pressure. This suggests that the structure of the blue compound may
be F,C10,ClF2 :
2FaC102F
+ F,ClO2ClF, +
0 2
+ FS
The formation of the blue compound may therefore be represented by the

equation :
OaFa
+ 2C1F --+
F,ClO,ClF2
The irradiation of a gaseous mixture of OF, and ClF, in a quartz flask leads
to the formation5*of the white, crystalline compound [ClOF,]$ [SiF,I2-. The
compound melts under its own vapour pressure at 50.8 OC and dissociates
into ClOF, and SiF,, which may be detected in the gas phase by mass spectrometry and i.r. spectroscopicmethods. The reaction of ClOF, with fluoride
ions, as a Lewis base, leads to the formation of the hitherto unknown oxotetrafluorochlorate ion, ClOF;:
C1OF8
+ CsF - i
20 C
Cs+ [CIOFJ-
The compound ClOF, may be prepared by the photochemical reaction of

ClF, and OF, in a nickel vessel fitted with a sapphire window; small amounts
of CIOF, are produced together with the compound C10F3.
Water.-An accurate, scale, two-dimensional model of the structure of liquid
. ~ ~ model shows that:
water at 20 C and 1 atm has been c o n s t r ~ c t e d The
(i) the distinction between mixture and continuum modes may be meaningless, (ii) clusters largely impinge upon other clusters and do not swim in
monomeric water, and (iii) by minor alterations in the hydrogen bonding, the
cluster model may readily be transformed into a broken down ice-type
structure or a more attenuated random network. A new model for liquid
water has been developed60 on the basis of the intermolecular potential
function proposed by Ben Naim and Stillinger and some simple and clearly
57
58
59
D. J. Gardiner, J. Fluorine Chem., 1973, 3, 226.

K. Zuchner and 0. Glemser, Angew. Chem. Internat. Edn., 1972, 11, 1094.
R. A. Courant, B. J. Ray, and R. A. Homer, J. Struct. Chem., 1972.13, 544.
0. Weres and S. A. Rice, J. Amer. Chem. SOC.,1972, 94, 8983.
Elements of Group V .
569
defined structural assumptions. A comprehensive survey (419 references) of

the literature on the subject of the so-called anomalous water has been
published;61the survey concludes that anomalous water is probably an artefact of preparation. The same conclusion has been reached by Derjaguin and
ChuraeP2 following careful neutron-activation analysis of samples of
anomalous water. All samples which exhibited anomalous behaviour were
found to contain impurities such as silicic acid, Na, Si, 0, K, and C1.
Published i.r. data for liquid water under a wide range of conditions, both
in the fundamental and overtone regions, have been examined63from the
specific viewpoint of proving or disproving the presence of detectable concentrations of water molecules not hydrogen-bonded to their neighbours.
Although all the results may be satisfactorily accommodated by a model in
which the H 2 0 molecule is bonded by 4 or 3 hydrogen bonds, this does not
necessarily constitute proof that monomeric water is not responsible for the
observed effects. New data for H 2 0 and HOD in the second overtone region,
10 000 cm-l, do seem to afford the required proof, and it now seems that the
concentration of monomeric water in liquid water is negligible. The vapour
pressure of HOD has been measureda between -60 and 20OoC. The v2
fundamental vibration-rotation band of T20 vapour has been measured65at
grating resolution and the rotational structure analysed. The values obtained
are consistent with those obtained by extrapolation from H20 and D,O. The
changes in separation of the stretching vibrations of water due to coupling
resulting from systematicvariations in the strengths of the hydrogen bond have
been measured.66
Low-energy electron bombardment of ice films has been shown6' to generate
water clusters on the surface. Clusters of the type H+(H20),, where 3 < n Q 8
at 193 K, were observed. The relationships between the various structures
adopted by ice have been investigated68by building structural models and
studying how the molecules must move and which bonds have to break or
form in order to progress from the ice 1, model through the sequence of unit
cells up to ice VII. MO calculations based on the CNDO approximation
have been reported69for hexagonal ice. The theoretical structural data are
found to agree well with experiment. The differences between bond angles for
gas-phase and crystalline water are interpreted in terms of the crystal polarization energy. Changes in i.r. and far4.r. spectra of vitreous water ice I, have
been observed70 at several temperatures between 92 and 210K during the
phase transition to cubic ice I,. Results of the phase transformation are also
M. P. Gingold, Bull. SOC.chim. France, 1973, 1629.
B. V. Derjaguin and N. V. Churaev, Nature, 1973, 224,430.
e3 L.M.Kleiss, H. A. Stroebel, and M. C. R. Symons, Spectrochim. Actu, 1973,29A,829.
64 W.A. Van Hook, J. Phys. Chem., 1972,76,3040.
ti6 R. A. Carpenter and N. M. Gailor, J. Mol. Spectroscopy, 1972, 44, 197.
66 L. J. Bellamy and R. J. Pace, Spectrochim. Actu, 1972, 28A, 1869.
67 G. R. Floyd and R. H. Prince, Nature Phys. Sci., 1972,240, 11.
O8 A. Von Hippel and E. F. Farrell, Mater. Res. Bull., 1973, 8, 127.
D. P. Santry, J . Amer. Chem. Soc., 1972,94,8311.
7 O A. H. Hardin and K. B. Harvey, Spectrochim. Acta, 1973,29A,1139.
62
570
reported for D,O ice I and HDO-bearing ices. Between 120 and 135K,
marked changes occurred in the structure of the spectrum as well as in the
wavenumbers, half-widths, and heights of the bands. The results indicated
that the vitreous to cubic ice I phase transformation occurred between 120
and 135 K and required less than eighteen minutes to reach equilibrium at
135 K.
A simple model has been proposed71for the structure of liquid water that
explains the concentration and temperature dependence of the Raman spectra
of water in water-dimethyl sulphoxide mixtures. The model proposes two
states for a hydrogen-bonded water molecule. One state involves a symmetrically hydrogen-bonded species which exhibits a symmetric OH stretching vibration that is i.r.- and Raman-active and an antisymmetric OH
stretching vibration that is active in the i.r. and anisotropic Raman spectra
but forbidden in the isotropic Raman spectrum. The other state involv2s an
asymmetrically hydrogen-bonded specieshaving two OH stretchingvibrations,
one of which involves the hydrogen-bonded OH and the other the weakly
hydrogen-bonded OH. Electrochemical and dilatometric studies have indi~ a t e that
d ~ ~at least three states of water may exist in macromolecular gels.
The proton chemical shifts of water in hydration complexes of the cations
Sn4+, A13+, Ga3+, In3+, Mg2+, and Be2+ have been measured73at low temperatures. A co-ordination number of 6 was found for Mg, Ca, Sr, and Ba,
4 for the alkali metals, zero for Me4Nf, and 4 for SO:-. The state of water in
inorganic crystal hydrates has been discussed74and the various distortions of
the water molecule, as far as its dissociation under the influence of the
environment, have been analysed. The reactions involved in the extensive
dehydration of crystalline hydrates have been examined from the viewpoint
of the relationship between the state of water on the hydrate and the characteristic features of the dehydration process. An explanation has been proposed7s
to account for the variation between the crystal structure of barium acid
oxalate dihydrate H2C2O4BaC2O4,2H20
and the bivariant equilibriumwhich is
formed with water vapour. The theory is based upon the weak bonding of the
water molecules which lie in zeolite-like channels in the structure. The water
molecules, although having precise crystallographic positions, contribute
only slightly to the cohesiveness of the crystal. On dehydration, therefore,
little structural modification is necessary. The possibility of using the dehydration of crystal hydrates as a means of purifying salts has been investigated.76*77
1.r. spectroscopy was used to study the dehydration by organic
71
72
73
74
75
J. R. Scherer, M. K. Go, and S . Kint, J . Phys. Chem., 1973,77, 2108.

M. Aizawa, J. Mizuguchi, S. Suzuki, S. Hayashi, T. Suzuki, N. Mitomo, and H.
Toyama, Bull. Chem. SOC.
Japan, 1972,45, 3031.
V. N. Makatum and L. N. Shchegrov, Russ. Chem. Rev., 1972, 905.
J. C. Mutin, G. Watelle-Marian, Y.Dusausoy, and J. Protas, Bull. SOC.
chim. France,
1972,4498.
76
77
N. Kolarov and M. Manerva, God. Vissh. Khimikotekhnol Inst. Sofia, 1968, 15, 191
(published 1972).
N. Kolarov and M. Manerva, Monatsh., 1973,104,685.
57 1
solvents of Na,SO,, 1OH20 containing non-isomorphous impurities (NaCI,
NaBr, NaI). The rate of dehydration was found to depend on the organic
solvent used and the nature of the impurities present in the salt. Mixing and
temperature were found not to affect the dehydration process appreciably.
The purification of Na,SO, by the dehydration of Na2S0,,10H20 is not
feasible at concentrations of NaCl, NaBr, and NaI impurities below 28, 64,
and 135 p.p.m,, respectively. The termolecular reactions of the 0- and OHions with water to produce O-,H20 and OH-,H20 have been studied7sin a
mass spectrometer. Rate constants of species and the bond dissociation
energy of OH-,H20 have been determined.
MO calculations by the INDO method have been performed79for the
H30*radical and some of its water complexes in an attempt to explain (a)
the formation of H,O. radicals from the reaction of hydrated electrons with
hydronium ions :
eaq
+ H@&
--j
H3O'sq
and (6) the subsequent decay:

H,O*au ---+
H.aq
+ HZO
The calculations indicate that the H30*

radical is stable against bond dissociation to H 2 0and hydrogen atoms, but unlike the ion, it is destabilized by the
surrounding water complexes. A previous report of the discovery of the e.s.r.
spectrum of the H30-radical in u.v.-irradiated perchloric acid glass has been
reinvestigated.80The e.s.r. spectrum previously assigned to H30*has been
shown to be identical to that of 'CH3. It is therefore concluded that the
existence of H,O' has not been experimentally demonstrated. MO-LCAO
methods have been useds1 to study the influence of external electrostatic
effects on the geometry of the hydroxonium ion H30+ in solids whose structures are known. Calculations have also been performed on the free ion,
where the energy minimum is found for a non-planar conformation with
HOH angles of 116.6' and O-H distances of 0.96 A. The eRect of the external
field is to lengthen the O-H distance and to decrease the HOH angle to form
approximately linear hydrogen bonds. A new model has been developedE2to
describe the chemical shifts of aqueous acid solutions which takes into account
the structure-breaking effect of ions. The model predicts the differing values
obtained from different acids for the chemical shift of N30+ and predicts
closely the temperature variations. The electronic field of H,O+ produces
only small chemical shifts in any hydrogen-bonded water, and n.m.r. chemicalshift studies are probably insensitive to the presence of other species such as
H,OS or H,O$. The problem of detecting the presence of OH groups in
B,03 by i.r. spectroscopy has been studied.83A differentiation has been made
C. E. Melton, J . Phys. Chem., 1972,76, 3116.
L. Efskind, Acta Chem. Scand., 1972,26,4147.
so S. Noda, H. Yoshida, and L. Kevan, Chem. Phys. Letters, 1973, 19, 240.
J. Almlof and U. Wahlgren, Theor. Chim. Acta, 1973,28, 161.
8a J. W. Akitt, J.C.S. Dalton, 1973,49.
83 P. Broadhead and G. A. Newman, Spectrochim. Acta, 1972,28A,1915.
78
7D
Inorgaiiic Chemistry of the Maimgroup Elements
572
between surface adsorbed OH groups and internal OH groups and a method

for the removal of the latter is described. The rate constant for the reaction of
H 0 2with CO has been founds4to be very much less than that for the reaction
of OH with CO. This is in conflict with a recent paperss that gave the two
reactions in the reverse order in terms of rate constant.
2 Sulphur
The Element.-Two reviews on the properties of elemental sulphur have been
published. The first deals86with new allotropic forms of sulphur as prepared
by the reaction of polysulphides with either S,CI, or SC12, the structures of
S,, S,, S8, S,, Sl0, S,,, S,,, and s18, and polysulphides up to Sg-. The seconds7
reviews sulphur modifications; sulphur rings containing heteroatoms and the
structures of sulphur molecular ions, melts, and vapours.
The crystal structure of a new form of elementary sulphur, sl8, has been
described.**The configuration of the molecule is a ring containing 18 atoms of
sulphur (1). The crystals have the typical green-yellow colour of sulphur and
n
crystallize in the space group P2,2,2,, with unit-cell dimensions a = 21.14,

b = 11.43, c = 7.58 A. The average sulphur-sulphur distance is 2.06 A with
a bond angle of 105.3" and a dihedral angle of 84.5' (average values). The
synthesis and crystal and molecular structures (2) of cycloeicosasulphur S,,
have been described.s9The crystals were found to belong to the orthorhombic
space group Pbcn with the unit-cell dimensions a = 18.580, b = 13.181,
c = 8.600A. Four molecules are contained in the unit cell. The average
sulphur-sulphur distance was 2.042 A, with the angle SSS equal to 106.4'.
Refinement of the crystal structure of orthorhombic sulphur has showng0
**
85
86
ST
88
@O
D. H. Volman and R. A. Gorse, J. Phys. Chem., 1972, 76, 3301.

A. A. Westenberg and N. de Haas, J. Phys. Chem., 1972,76, 1586.
M. Schmidt, Chem. unserer Zeit, 1973, 7 , 11.
M. Schmidt, Angew. Chem. Internat. Edn., 1973, 12, 445.
T. Debaerdemaeker and A. Kutoglu, Nuturwiss., 1973, 60,49.
T. Debaerdemaeker, E. Hellner, and A. Kutoglu, Nuturwiss., 1973, 60, 300.
G. S. Pawley and R. P. Rinaldi, Act0 Cryst., 1972, B28, 3605.
573
s-s
that there is a considerable distortion of the s8 molecules on forming a

crystal. Although the diffraction data are fitted very well by a rigid-bodymotion model, it is thought that the motion is not, in reality, of the rigidbody type. The Raman spectrum of gaseous S2at 718 cm-l has been reported.g1
A resonance fluorescence series of gaseous 32S,(excited by the 5145 Ar+ laser
line) was analysed in detail. Spectra of matrices containing S , have showng2
the presence of an absorption at 530 nm which is characteristic of the molecule
S,. Also observed was a very weak absorption around 625nm, which was
thought to belong to a transient species that was probably S, molecule
chains or S, molecule rings. The i.r. and Raman spectra of cycloheptasulphur
have been reported.93The fundamentals were assigned in terms of Cssymmetry and compared with those of the molecules S8 and S6. Force-fields
transferred from s8 and S, provided fair agreement between the calculated and
experimental frequencies of S,. Cycloheptasulphur exists as a puckered sevenmembered ring, and the only symmetry element the molecule may possess is a
mirror plane. Whilst the various phases of solid sulphur have been extensively
studied, much less is known concerning the structure of sulphur vapour. A
photoelectron spectroscopic studyM of sulphur vapour, excited by He I
radiation, at a temperature just above the melting point has yielded useful
information. The available data were found to require a cyclic, nonplanar,
fairly rigid structure with a ring size of five or more. From integrated peak
intensity data, the species was found to be cyclic octasulphur. A consideration
of the lone-pair ionizations ruled out cradle, butterfly, tub, chair, and other
less symmetrical C, configurations, and only the crown D4d conformation
was considered suitable. An interpretation of the X-ray emission spectrum of
the molecule s6 has been carried outg5on the basis of CND0/2 calculations.
The chemical shifts of the sulphur K, lines in different compounds have been
measuredg6to high accuracy using an X-ray vacuum spectrometer. The data
91
92
93
94
K. K. Yee, R. F. Barrow, and A. Rogstad, J.C.S. Faraday 11, 1972, 68, 1808.
B. Meyer and T. Stroyer-Hansen, J. Phys. Chem., 1972,76, 3968.
M. Gardner and A. Rogstad, J.C.S. Dalton, 1973, 599.
R. Bosch and W. Schmidt, Znorg. Nuclear Chem. Letters, 1973, 9 , 643.
H. C. Whitehead and G . Andermann, J. Phys. Chem., 1973,77, 721.
G . Leonhardt, P. Pelowa, and A. Meisel, 2.anorg. Chem., 1973, 397,209.
574
from the charge distribution, obtained from the sulphur K, shifts, are comparable to those obtained from photoelectron spectroscopy studies and with
values obtained from MO calculations.
The electrical conductivity of molten sulphur at temperatures up to 200 O C
has been studiedg7on samples which were specially purified, as well as doped
with impurities (paraffin, phenanthrene, benzidine, bromine, and iodine).
The current flow below 160 "C results from electrophoretically migrating
impurities and, by interaction with the impurities, ionized molecules, whereas
at higher temperatures conduction is caused by electrons. At the minimum of
viscosity of the molten sulphur (154.5 "C)the conductivity shows a maximum,
which is shifted by impurities (especially halogens) as much as 10 "Ctowards
lower temperatures. The effect on the mechanical properties of sulphur by the
presence of S, has been studied.98The preparation (3 methods), identification,
and testing of S, are reported. Specimens with an S, content of more than
16 % may be prepared by pouring hot sulphur into cold CS2. An analysis of
the results of the study indicates that S, acts as a typical low-modulus material,
binding the high-tensile-strength, high-modulus sulphur crystals together. A
layer of sulphur, produced on a platinum electrodeby anodic electrodeposition
from an alkali-metal thiocyanate melt, has been showng9to give a marked
photoelectric effect with visible light in solutions of melts containing S2- ions.
The photoelectric activity is thought to form small amounts of thiocyanate
ions either adsorbed on the electrode surface between sulphur atoms or
occluded in the bulk of the sulphur phase. The electrons set free by light, as
charge carriers in the sulphur layer, move away from the sulphurlsolution
interface towards the metal, and, at the same time, more sulphide ions from
the solution are discharged at the electrode. In consequence, the electrode
changes its potential to a more negative value or, the anodic current of
sulphur deposition increases.
A method for the generation of variable and accurately determined partial
pressures of sulphur has been described.loOThe technique enables the study
of the thermodynamic and electrical properties of metal-sulphur systems at
high temperatures to be carried out and has application to studies of phase
diagrams, non-stoicheiometry, electrical conductivity, and of the Seebeck
effect. The precision of the stability of the sulphur pressures obtained is controlled by direct determination at high temperatures, using a manganese
sulphide probe.
Spectrophotometric observations, electrochemical data, e.s.r. spectra, and
cryoscopic measurements on solutions of sulphur in liquid ammonia have
been reported.lol The data indicate that the sulphur species present at low
F. FCher, R. Heider, D. Barnert, and H. D. Lutz, 2.anorg. Chem., 1973,399, 77.
A. C. Ludwig and J. M. Dale, Sulphur Ins?. J., 1973, 9, 10.
Bs F. Pucciarelli, P. Cescon, F. Diomedi-Camessei, and M. Heyrovsky, J.C.S. Chem.
Comm., 1973, 154.
looJ. P. Delmaire and H. Le Brusq, Bull. SOC.chim. France, 1973, 879.
lol A. Kerouanton, M. Herlem, and A. Thiebault, AnaZyt. Letters, 1973, 6 , 171.
97
98
575
temperatures is S2NH, and SNH, is the predominant species at room temperature. The vapour pressures of sulphur over sulphur-thallium liquid
mixtures (0.55 to 0.98 mole fraction sulphur) have been measured.lo2Although
the mixture is quite stable at the composition T12S, the sulphur activity is
quite high and its partial molar heat of solution is positive in the intermediate range. This result is interpreted in terms of a modification of the
sulphur chain on the addition of thallium; the change being from S, through
TI-SB-Tl
to Tl-S-T1
(TI$).
The e.s.r. spectra of thermally coloured hackmanites (yellow-green at
800 "C,light blue at 950 "C,blue at 1100 "C)and of green, sky-blue, and blue
lazurites have been measuredlo3at room temperature. The results confirm
the formation of S F , SOT, SSO- colour centres. Measurements of the relative
concentrations of S,, following flash photolysis of COS diluted with carbon
dioxide, have been usedlo4to investigate the mechanism of the polymerization of sulphur atoms. The formation and removal of Sz occurs primarily by
the following mechanism:
2s,
s, + cos
s + s4 4 s, + s,
s + ss 2s*
+ COZ
A thermogravimetric method has been usedlo5to investigate the kinetics of

reaction of tungsten metal with pure sulphur vapour at temperatures between
295 and 550C. The rate of sulphurization of the metal was rapid and increased systematically with temperature to a rate maximum at 46-75
"C;
thereafter the rates decreased. The initial sulphurization rate increased, in a
complex manner, with increasing sulphur pressure for temperatures below the
rate maximum; above this temperature the rate increased directly with the
partial pressure of S2. Tungsten disulphide was the only reaction product
detected under all experimenta1 conditions.
Sulphides.-The crystal chemistry of the sulphides of both the Main-group
and the Transition elements has been reviewed.lU6The Gibbs free energy of
formation as a function of temperature has been derivedlo7from published
data for some 29 sulphides. Using the extended Hiickel MO method, the
origin of the conformational preference of acyclic disulphides has been
elucidatedlosfor the molecules HSSH and H,CSSCHS. Overlap population
between the sulphur atoms is greatest when the dihedral angle about the S-S
Fukuda, T. Yokokawa, S. Nagai, and K. Niwa, Trans. Japan. Inst. Metals, 1972,
13, 352.
lo3V. P. Belichenko, V. V. Mazykin, A. N. Platonov, and A. N. Tarashchan, Dopovidi
Akad. Nauk Ukrain. R.S.R., Ser. B, 1973,35, 99.
lo4R. B. Langford and G. A. Oldershaw, J.C.S. Faraday I, 1973, 69, 1389.
lo6J. E. Dutrizac, J. Less-Common Metals, 1973, 31, 281.
lo( U. V. Shcherbina, Geokhimiya, 1972, 1035.
lo' M. Fr. Ancy-Moret, Mem. Sci. Rev. Met., 1973, 70, 429.
lo*D. B. Boyd, Theor. Chirn. Actu, 1973, 30, 137.
loaN.
576

bond is near 90, since the negative contributions from the repulsive interactions of the lone-pair electrons are at a maximum. Electron-density maps
are used to illustrate the rearrangement of the valence electrons in HSSH
when the molecule is formed from the isolated atoms and thc redistribution
which takes place when the molecule is twisted about the S--S bond.
Sukhides of Group I, 11, and 111 Metals. Equilibrium phases in the litkiumsulphur system on the sulphur-rich side of Li2S have been determined by an
unusual vapour-transport technique.logIn this method the equilibrium compositions of the melts at various temperatures can be obtained by utilizing
the transport of sulphur vapour from one melt to a second one. The lithiumsulphur system exhibits a large miscibility gap from the monotectic composition of 65.5 mole % S to almost pure sulphur. The melting point of lithium
sulphide, Li,S, was found to be 1365 f 10 "C. A comparison of the liquidus
at the Li,S liquid region with those constructed by a model indicates the
probable existence in these melts of sulphide species such as Si-, S:-, and
Si- in addition to the expected S2-. A second studylf0of the same system has
shown the presence of a miscibility gap from 0.2 to 37 at. % Li above a monotectic temperature of 364.8 "C.The only compound observed was the sulphide
Li,S, with a melting point of 1372 "C.Attempts to gain a better understanding
of the reactive species in the sodium-sulphur battery system have led to a
re-examinationlll of the sodium-sulphur phase diagram first published112 in
1930. Differential thermal analysis was used to construct the phase diagram
(Figure 1) and showed, in addition, that when mixtures of Na,S and Na2S,
or Na2S4and S8 are heated, a reaction takes place around the melting point of
sulphur, with the formation of the pentasulphide Na2S, as the initial step.
Unless the sodium:sulphur ratio in the mixture is 5 ; 2 or higher, further
interaction between the sulphides can be observed, until at equilibrium only
those species are observed which correspond to the given stoicheiometric
Na: S ratio. The highest sulphide found was Na2S5,whereas the trisulphide
Na,S, does not exist at the melting point, and the mixture with the same
stoicheiometry was found to be a 1 :1 Na2S-Na,S4 eutectic. A novel method
for the synthesis of the sodium polysulphides in liquid ammonia has been
described,l13 based on the reaction scheme:
2NaCl
+ K,S,
2KC1
+ Na,S,
(x = 3, 5 , or 6)
The polysulphides Na,S3 and Na2Ss were prepared, but not Na2S,. The
hitherto disputed Na,S, decomposes at 100 "C into a mixture corresponding
to the 1 :1 eutectic Na2S2-Na2S4.It was concluded that sodium hexasulphide
does not exist, and efforts to prepare the compound resulted in the formation
log
11*
112
113
R.A. Sharma, J . Electrochem. SOC.,1972,119,1439.

P. T. Cunningham, S. A. Johnson, and E. J. Cairns, J. Electrochem. SOC.,1972, 119,
1448.
D. G. Oei, Inorg. Chem., 1973, 12,435.
T. G.Pearson and P. L. Robinson, J . Chem. SOC.,1930, 1473.
D.G. Oei, Inorg. Chem., 1973, 12,438.
577
Two Liquids
t-
300
Liquid
200
Liquid
I00
u
60
70
80
SULFUR, W T
Na2S5( Satd.1
Liquid Sulfur
90
Figure 1 Phase diagram of the Na-S system between the compositions Na,S2
and 100%S
of Na,S, and sulphur. Samples of cc-Na2S2,K,S,, Na2S4,and Na,S, have been
studied by ESCA. The binding energies for the sulphur 2p electron in the
polysulphides were found to be 162.5 eV for the So state and 159.7 eV for the
S- state. The observed ratios of the relative intensities of the sulphur 2p
electrons for the So and S- state were thought to provide direct and unequivocal evidence that the polysulphide chain has the unbranched structure,
This conclusion has been verified again in a crystal structure deterrninati~nll~
of sodium tetrasulphide, Na,S,. The compound crystallizes in the tetragonal
space group Iif2d, with the cell dimensions a = 9.5965, c = 11.7885 A and
llP
R. Tegman, Acta Cryst., 1973, B29, 1463.
578
2 = 8. The structure is built up of unbranched Si- ions surrounded by Naf
ions. The distance between different Si- ions was found to be about 3.60 A.
The Si- ions lie on a two-fold axis, with sulphur-sulphur bond distances of
2.074 A (end), and 2.061 A (middle), a SSS bond angle of 109.76', and a
dihedral angle of 97.81". The sodium-sulphur polyhedra co-ordination
consists of two types, a distorted tetrahedron, with two pairs of distances of
2.826 and 2.842 A, and a distorted octahedron, with three pairs of distances
of 2.887, 3.043, and 3.081 A. The potassium pentasulphide K2S5 has been
prepared115 by the reactions :
+ HZS -+ C2HjjOH + HSK+ + HS- + 2s

BKzS6 + 4HZS
C2HoO-
The entropy of K,S was found to be S298.15

= 61.4 Gibbs and the powder
pattern of the compound was indexed on a triclinic unit cell with a = 7.4,
b = 13.55, c = 13.975 A; cc = 118'59', B = 85"16', and y = 94'45'. The
unit cell was thought to have a hexagonal character, with a = 13.76, c =
7.40 A.
Alkaline-earth metal sulphides have been prepared116 by hydrogen reduction of the metal sulphate at high temperatures. Calcium sulphate was
reduced at 2850 ' C , with strontium and barium sulphates being reduced at
2 9 5 0 'C. The products of the reduction were said to be uniform and to contain about 98% sulphide. A method has been describedll' by which the
sulphides CaS, SrS, and Bas may be prepared by the reaction of the metals in
solution in liquid ammonia with an excess of hydrogen sulphide at temperatures ranging from -78 to -33 O C in high vacuum. Analytical data and
lattice parameters of the sulphides prepared in this way were given.
A new modification of indium sulphide, y-In$,, has been preparedlls by
a vapour-phase deposition method. X-Ray, topographical, and electron
microscopy studies were carried out and the compound was found to decompose by the loss of sulphur in the electron microscope. The molecular
constants of BS, have been determined1l9from a study of the i.r. spectrum
obtained at 4 K from the solid, trapped in neon matrices.
Group IV Metal Sulphides. The core-level electron spectrum of CS,, excited
by Mg Ka radiation, has been studied120 to identify shake-up satellite lines
associated with ionizations from these levels. A number of such lines were observed and possible assignments suggested using the excited states of the
molecule as a guide. The valence spectra were also recorded and they too
were found to be rich in shake-up structure. The photoelectron spectra of
M. Diot, J.-M. Letoff, M. Prost, and J. Bouquet, Bull. SOC.chim. France, 1972, 4490.
E. Pedak, M.Allsalu, and M. Kanter., Zhur. priklad. Khim.,1972, 45,2619.
11' T. Petzel, 2. anorg. Chem., 1973, 396, 173.
11* P. Buck, J. Appl. Cryst., 1973, 6 , 1.
llS J. M. Bromje and W. Weltner, J. Mol. Spectroscopy, 1973, 45, 82.
l * O C. J. Allan, U. Gelius, D. A. Allison, G. Johansson, H. Siegbahn, and K. Siegbahn,
J. Electron Spectroscopy, 1972, 1, 131.
11(
Elements of Group Vl
579
CS2, H,O, and H2S have also been rneasuredl2l as a function of the angle
between the direction of the incoming photon and outgoing photoelectron.
The i.r. spectra of liquid CS, in the range 300-10 000 cm-l and CS, in CCI,
in the range 300-5000 cm-l have been measured.122In solution the bands
become narrower, revealing in some instances well-developed 'hot' side-bands.
The effects of dilution and change of temperature on the Raman spectrum of
CS, have been studied.123The fluorescence of CS, vapour has been measured124
as a function of both wavelength of excitation and wavelength of fluorescence.
The X-ray K emission and absorption spectrum of CS2 have been investigated125in order to determine the electronic structure of the CS, molecule.
The strongly Raman-active S-S stretching mode between 498 and 511 cm-l
in a variety of disulphides has been shown126to be independent of the dihedral CSSC angle from 20 to near 90'.
Solid silicon monosulphide in an amorphous form has been prepared12' by
the condensation of gaseous SiS at high temperatures. Vaporization and
vapour pressure data suggest that SiS is metastable, disproportionating into
SiS, and silicon at an appreciable rate above 950 K. SiS appears to be thermodynamically unstable below 1452 K. Vaporization of solid SiS, yields predominantly SiS and S, species according to the dissociation process:
siszw,
SiSW
+ 3Sz(e,
Partial pressures of SiS and other sulphur species were measured over the
temperature range 991-1 122 K and used to compute the standard free-energy
change of the reaction. The molecular and crystal structures of tetra(methy1germanium)hexasulphide have been determined.128The crystals are monoclinic, space group C2/c, with a = 9.422, b = 16.779, c = 10.708 A; =
107.94', and 2 = 4.The molecule was found to adopt the adamantane (3)
rather than the open-cage structure (4), both of which have previously been
lZ1
laa
1*3
lZ4
la5
lZ8
T. A. Carlson and G. E. McGuire., J . Electron Spectroscopy, 1972, 1, 209.

S. B. Ribnikav and 0. S. Puzic, Spectrochim. Acta, 1973, 29A, 307.
J. A. Creighton and T. J. Sinclair, Spectrochim. Acta, 1973, 29A, 817.
C. Lambert and G. H. Kimbel, Canad. J. Chem., 1973, 51,2601.
L. N. Muzalov, A. P. Sadovskii, V. M. Bertenev, K. E. Mironov, T. I. Guzhavina,
and L. N. Chernyavskii, J . Struct. Chem., 1973, 14, 802.
E. J. Bastian and R. B. Martin, J. Phys. Chem., 1973, 77, 1129.
J. J. Byerley and W. K. Teo, J. Inorg. Nuclear Chem., 1973, 35, 2195.
R. H. Benno and C. J. Fritchie, J.C.S. Dalton, 1973, 543.
38
580
suggested for (MeGe),S,. Every germanium atom in the structure (5) is
H.11
bonded to three sulphur atoms and one carbon atom, which are located at
the corners of a slightly distorted tetrahedron. Mean bond distances and
angles are Ge-S 2.218, Ge-C 1.922A, LSGeS 118.8", LGeSGe 104.6',
and LSGeC 107.0".
Mossbauer spectra have been reported129for the tin sulphides SnS, Sn3S4,
Sn,S,, and SnS,. The spectra observed for the compounds Sn3S4and Sn,S,
may be represented as a superposition of spectra characteristic of SnS and
SnS,. At 480 K the heat (AH, = 23.4 kcal mol-l) and entropy ( A S =
- 1.2 cal mol-l degree-l) of formation of PbS have been measured130 by
differential thermal calorimetry for the reaction :
Pb(s1
+ S(1)
4 PbSte,
Group Y Metal Sulphides. The sulphur-red phosphorus phase diagram and

the metastable sulphur-white phosphorus system have been studied131 by
means of differential thermal analysis between -100 and +600"C. Seven
different phosphorus sulphides were characterized, uiz. P4S10, P4S9, P4S7,
P4S5,PS, P4S3,and P,S. The compounds P4S10, P4S7,and P4S3were found to
have both high- and low-temperature modifications. A more detailed study132
of the non-congruently melting phosphorus sulphides P4S9 and P4S4 has
shown that they may be prepared by the following general method. A mixture
of red phosphorus and P,S,, is heated to melting, allowed to solidify slowly,
lag
130
131
132
P. P. Seregin, M. Sagatov, B. T. Melekh, Yu. P. Kostikov, and L. N. Vasilev, Izuest.

Akad. Nauk S.S.S.R., Neorg. Materialy, 1973, 9, 134.
M. S. Shamsuddin, Current Sci., 1973, 42, 119.
H. Vincent, Bull. SOC.chim. France, 1972, 4517.
H. Vincent and C. Vincent-Forat, Bull. SOC.chim. France, 1973, 499.
581
and the products are then extracted by recrystallization from CS2 at room
temperature. The sulphide P4S2 may be prepared from a mixture of P4S3and
white phosphorus. X-Ray data and heats of formation were determined and
the molecular structures (6), (7), and (8) were proposed.
P-
-P
1.r. and Raman spectra of the four crystalline sulphides P4S3, P4S5, P4S7,
and P4Sl0have been recorded133 in the solid state. The Raman spectra of the
melts formed by all four compounds and of the vapours formed from P4S3,
P4S7,and P4SIo were also recorded. Only P4S3retains the same structure in all
three phases. P4S5disproportionates in the melt to P4S3and P4S, and further
species that were not identified. Both P4S7and P4S10 lose terminal sulphur
atoms in the gas phase. The Raman spectrum of sulphur was found to obscure
the spectrum of the remaining phosphorus-sulphur species. The melt spectra
of P4S7and P4Sl0were identical to the solid-state spectra, but the dark colour
observed for the melt suggests that some terminal sulphur is dissociating. A
highly stereospecific, single-step transformation of tertiary phosphine oxides
into phosphine sulphides by boron trisulphide has been reported.13*
The experimental radial distribution curves of vitreous As2S3and As2Se3
have been interpretedBs in terms of a lamellar structure. Each layer in the
structure consists of bands formed by five atom rows, with the nearest
neighbours being unlike atoms. The vapour pressure of As2S3,in the NaAsS,Na3AsS, system and over Na3AsS3,has been determined136in the temperature
regions 370-659 and 780-94O0C. The vapour pressure observed in the
NaAsS2-Na3AsS3 system was lower than that found over pure Na3AsS3
owing to solution formation. The compound Na,AsS, was found to decompose at 947 OC at 760 Torr. The saturated vapour pressure of solid ASS has
133
134
135
M. Gardner, J.C.S. Dalton, 1973, 691.

B. E. Maryanoff, R. Tang, and K. Mislow, J.C.S. Chem. Comm., 1973, 273.
Yu. G. Poltsavtsev, V. M. Pozdnyakova, and V. P. Rubstov, Ukrain. fiz. Zhur., 1973,
18,915.
136
A. N. Polukarov, M. I. Zhambekov, M. Zh. Makhmetov, and S. N. Isabaev, Trudy

Khim. Met. Inst, Akad. Nauk Kazakh. S.S.R., 1972, 19, 23.
582

been recorded13' at 432-548 K by the Knudsen method. The heat of sublimation of As,S, at 490 K is 28.5 kcal mol-l and the heat of fusion of ASS
was found to be 2.8 kcal mol-l. The Raman and i.r. spectra of single crystals
and glassy samples of As,S, have been measured.138 The crystal structure of
synthetic p-dimorphite, As&, has been determined139by a three-dimensional
single-crystal X-ray study from photographic data. The crystals are orthorhombic, space group Pnma, with 2 = 4 in a unit cell of dimensions a =
11.21, b = 9.90, and c = 6.58 A. The structure (9) is built up of As4S3
molecules, similar to those observed in the a-form, with C,, symmetry. The
bond angles and distances are not significantly different from those of the
a-form. The shortest intermolecular As-As and As-S distances in /?-Asps3
are 3.83 and 3.47 A, compared with values of 3.60 and 3.47 A in the a-form.
None of these values are thought to indicate strongly directional intermolecular bonding.
The crystal structure of tetra-arsenic pentasulphide, AsqS5, has been

determined.140The crystals are monoclinic, of space group P2,/rn, with 2 = 2
in a unit cell of dimensions a = 7.98, b = 8.10, c = 7.14A; = 101.Oo.
The structure (10) is built up of discrete As$, molecules of approximate C,,
symmetry with As-As = 2.55 8, and mean As-S = 2.24 8,. The structure
of As& is quite different from those of P4S5and P,Se,, which have an exocyclic sulphur and selenium atom, respectively, double-bonded to a quinquevalent phosphorus atom.
Solid S,(AsF,), has been shown141to react with gaseous tetrafluoroethylene
at room temperature and moderate pressure to give arsenic trifluoride,
137
138
139
140
141
G. G. Gospodinov and A. S. Pashinkin, Izvest. Akad. Nauk. S.S.S.R., Neorg. Materialy,

1973, 9, 15.
M. P. Lisitsa, M. Ya. Valakh, L. I. Berezhinskii, and V. I. Sheka, Ukrain. $2. Zhur.,
1973, 18,98.
H. L. Paige and J. Passmore, Inorg. Chem., 1973, 12, 593.
583
bis(perfluoroethy1) di-, tri-, and tetra-sulphides, and, in some cases, traces of

penta- and hexa-sulphides. Substantially the same results are obtained when
the reaction is carried out in the presence of liquid SOF, and S02F2,in which
S,(AsF,), is not detectably soluble at 0 'C. It is thought that reaction may be
initiated by interaction between a weak transannular bond in the sulphur
cation and tetrafluoroethylene. The intermediate (1 1) may then abstract
a fluoride ion from a hexafluoroarsenate ion to form a perfluoroethylsulphur ion. The reaction of tetrafluoroethylene with this species followed
by fluoride-ion abstraction from a hexafluoroarsenate ion leads to the formation of bis(perfluoroethy1) polysulphides. The reaction of S,(AsF,), and
tetrafluoroethylene in SO2gave, in addition to AsF, and bis(perfluoroethy1)
polysulphides, C,F,S,CF,, C2F,S,CF,COF ( x = 2 or 3), CF,COF, and
SOF,. The reaction is clearly more complex than the previous reactions and
would appear to involve reaction with the solvent.
The characteristic features of the crystal structures of antimonite, Sb,S3,
have been discussed142 in terms of the 18-electron configuration. Thermal
annealing patterns of some neutron-irradiated thio-antimony compounds
suggest143that the trapping of metastable species is determined, in part, by the
142
143
N. V. Belov, Yu. G. Zagal'skaya, and E. A. Pobedimskaya, Doklady Akad. Nauk

S.S.S.R., 1973,209, 1330.
J. F. Facetti and A. Vallejos, J. Inorg. Nuclear Chem., 1972, 34, 3659.

matrix of the compound, and that the stabilization of the higher oxidation
state is related to the sulphur atom content and the covalent nature of the
Sb-S bond. The temperature dependence of the heat capacity of the ferroelectric semiconductor SbSI has been studied.14
Other Metal Sulplzides. The equilibrium between stoicheiometric TaS, and a
non-stoicheiometric phase TaS,., has been e~tablishedl~~
by measurement of
the electrical properties of compositional isotherms with the vapour pressure
of sulphur between 900 and 1200 "C. The rules governing the formation of
stable structures in the series of ArrBV1compounds (ZnO, and chalcogenides
of Zn and Cd) have been discussed.146 It has been shown that the crystalstructure type of the stable modification (sphalerite or wurtzite) and the degree
of ideality of the wurtzite lattice depends on the ratio of ionic to covalent
character of the bonding in these AI1BIV compounds. The conditions
necessary for the preparation of both single-crystaland polycrystallinesamples
of Gd,S3 have been described.14' Conditions have also been givenlg8for the
preparation of ternary metal chalcogenide halides for Sb, Pb, and Bi, by the
reaction of mixtures of the respective elements, binary components, or both,
in the appropriate hydrogen halide acid under hydrothermal conditions at
temperatures in the range 100-500 "C.
Ternary Sulphide Phase Systems. The equilibrium diagram of the Na,S-NaOH
system has been studied149 by d.t.a., X-ray diffraction, and microscopic
analysis. Two compounds were observed, namely Na,S,NaOH, which melted
congruently at 975 "C, and Na2S,2NaOH, which melts with decomposition at
675 O C . The liquidus shows two eutectic points at NaOH 37 mole % (735 "C)
and NaOH 95.5 mole% (255 "C).A
of the Na,S-SnS, system has
shown the presence of four crystalline phases Na4SnS4,Na,Sn,S,, Na2SnS3,
and Na4Sn3S8,which were characterized by X-ray powder diffraction. A
single crystal of the compound Na4SnS, was obtained and found to have
tetragonal symmetry with space group P421c; a = 7.837, c = 6.950 A, and
2 = 2. The compound Na,SnS, exists in two temperature modifications with
a transition temperature of 540 "C. The low-temperature form of Na,SnS,
was found to be monoclinic, space group C2/c or C / c , a = 6.640, b = 11.499,
c = 13.439 A; /i'= 99.47'; and 2 = 8.
The Na,S-As,S, system has been studied151by thermal, X-ray, and chemical
analyses, at temperatures less than 870 "C. D.t.a. curves were obtained and
compared for Na,S, AS$,, NaAsS,, Na,AsS,, and 1 :1 , 2 : 1, and 3 :1 mixtures
584
144
146
146
14'
148
IL8
lS0
lS1
S. A. Taraskin, V. A. Lyakhovitskaya, and A. K. Ivanov-Shits, Soviet Phys. Cryst.,

1972, 17, 597.
H. Le Brusq and J.-P. Delmaire, Compt. rend., 1973, 276, C, 1449.
IS.V. Shalimova and V. A. Dmitriev, Soviet Phys. Cryst., 1972, 17,470.
A. W. Sleight and D. P. Kelly, Znorg. Synth., 1973, 14, 152.
A. Rabenau and H. Rau, Inorg. Synth., 1973,14, 160.
E. V. Ovechkin, L. N. Shevtsova, A. E. Voitsekhovskii, L. I. Obomaya, and L. V.

Kuznetsov, Rum. J. Znorg. Chem., 1973, 18, 571.
F. Vermot-Gaude-Daniel and J. C. Jumas, Compt. rend., 1972, 275, C, 741.
M. I. Zhambekov, S. M. Isabaev, A. N. Pomkarov, and E. A. Buketov, Trudy Khim.
Met. Znst., Akad. Nauk Kazakh. S.S.R., 1972, 19, 16.
585
of Na,S and As,S, in argon atmospheres. In mixtures of anhydrous Na,S and

As,S, the formation of NaAsS, was observed as an exothermic effect at 80150 OC. The formation of Na,AsS, proceeded at temperatures greater than
480 "C. Irrespective of the initial composition of the reagents, the reaction
between Na,S and As.$, proceeded by, firstly, the formation of NaAsS, at
80-130 "C, followed by further reaction at 430-510 "C to give Na,AsS,.
Na,AsS, melts at 500-520 "C and is stable up to 800 "C;in the presence of
As,S, the melting point decreases to between 440 and 505 "C. S t ~ d i e s l ~ ~ - l ~ ~
of the Na-Sb-S system have shown the existence of the ternary compounds
NaSbS,, Na,SbS,, Na,SbS4, and Na$b,S,.
Polymorphic transformations
have been observed for the compounds Na,SbS, and NaSbS, at 495 and
580 "C, respectively. A study 155 of the systems As,Ss-NaOH-H20 and
Na3AsS4,8H,0-NaOH-H,O at 25 "C has led to the characterization of the
compounds Na3AsS4,8H,0 and Na3As02S2,11H20.The equilibrium diagram
of the In2S3-Sb2S, system has been studied;lS6In2S,,3Sb,S3, In,S,,Sb,S3, and
a range of solid solutions between indium sulphide and In,S,,Sb,S,, extending
from 90 to 100 mole% In2S3, are formed. The equilibrium diagram of the
quasi-binary system Cu,S-GeS, has been e~tab1ished.l~'Two definite compounds Cu2GeS, and Cu,GeS, were observed. Cu,GeS3 has a monoclinic
superstructure based on a deformed blende type structure. Cu8GeS, exhibits
two temperature-dependent forms, a low-temperature monoclinic phase and
a high-temperature cubic phase, with a transition temperature of 55 OC and a
transition enthalpy of 1.7 kcal mol-l.
Ternary SuIphide Compounds.The compound Bi,In4S, has been synthesized by
chemical transport reactions using iodine in the gas phase.158The crystal structure of the compound consists of a sulphur framework forming close packing
only in a prismatic domain parallel to theb-axis. Three indium atoms are in octahedral co-ordination by sulphur atoms, one of the octahedra being distorted.
The fourth indium atom is in a distorted tetrahedral environment.The six- and
seven-fold co-ordination of the two bismuth atoms by sulphur is related, only
in a broader sense, to that observed in Bi,S3. The compounds Na4Ge,S,,14H,0
and Na4Sn2S,,14H,0 have been prepared159in a pure state. X-Ray diffraction
has shown that the trithiogermanates M2GeS3and trithiostannates M,SnS,
previously described in the literature are in fact compounds containing dimeric
Ge&- and Sn,Si-ions. These ions are formed from two tetrahedra joined by
16a
V. G. Kuznetsov, A. S. Kanishcheva, and A. V. Salov, Russ. J. Znorg. Chem., 1972,
153
17, 129.
A. V. Salov, S.I. Berul, V.
1972,17, 1758.
B. Lazarev, and A. S. Kanishcheva, Russ. J. Inorg. Chem.,
V. B. Lazarev, A. V. Salov, and S. I. Berul, Russ. J. Znorg. Chem., 1973, 18, 112.
M. Palazzi and H. Guerin, Bull. SOC.chim. France, 1973, 851.
158 N. M. Kompanichenko, I. S. Chaus, V. D. Sukhenko, I. A. Sheka, and V. N. Lugin,
Russ. J. Inorg. Chem., 1973, 18, 569.
15' M. Khanafer, J. Rivet, and J. Flahaut, Bull. Soc. chim. France, 1973, 859.
15* G. Chapuis, Ch. Gnehm, and V. Kramer, Actu Cryst., 1972, B28, 3128.
150 B. Krebs, S. Pohl, and W. Schiwy, 2.unorg. Chem., 1972, 393, 241.
lS4
155
586
sharing a common edge (12). The compounds Na4Ge2S,,14H20 and

Na4Sn2S6,14H,O, which contain these new types of inorganic tetrahedral ions,
are isotypic, crystallizing in the triclinic system, of space group PI. In the
M2Si- ion the terminal metal-sulphur bonds are significantlyshorter than the
bridge bonds in the strained four-membered ring; 2.17 against 2.72w for
Ge-S, and 2.332 against 2.450 for Sn-S. The extensive OH. - .O and
OH. .S bridge systems of the two salt hydates were completely analysed.
An X-ray diffraction analysis of the compound Na,SnS4 has shown160 the
0
0
Atomic Co-ordinates
x/a(o)
YlW
ZlCW
Sn
0.0
0.0
0.0
0.0922(4)
0.2376(5)
0.1883(7)
B(4/A2
1.39(4)
1.56(6)
2.42(14)
Na
0.1997(8)
0.5910(9)
0.0313(11)
Figure 2 Projection along the b-axis and atomic co-ordinates of the structure
of Na,SnS,
(Reproduced by permission from Cryst. Struct. Cumm., 1973, 2 , 157)
160
J. C. Jumas, F. Vermont-Gaude-Daniel and E. Philippot, Cryst. Sfrucf. Comm.,

1973, 2, 157.
587
compound to be tetragonal, space group P42c, with lattice parameters
a = 7.837, c = 6.950 A, and 2 = 2. The crystal structure (Figure 2) is
built up from discrete orthothiostannate tetrahedra. The packing of these
SnS:- groups with the sodium ions is determined chiefly by electrostatic
interactions and the geometry of the system. The tetrahedra show only minor
deviations from regularity, the tin atom being located in a 4 point-symmetry
position with a tin-sulphur bond distance of 2.388 A. The sodium ions are in
five-fold co-ordination, with sodium-sulphur bond distances between 2.787
and 3.094 A. The structure of BaSnS, has been
The compound
crystallizes in the monoclinic space group P2,/c, with the cell dimensions
a = 6.0848, b = 12.1396, c = 6.2356A; #? = 97.058". The structure is a
distortion of the sodium chloride structure and can be considered as a composite of the Bas and SnS structures, both of which are based on the sodium
chloride motif. The barium atoms are in six-fold co-ordination at the centre
of a slightly distorted octahedron. Each tin atom occupies a distorted octahedral void but is close to a triangular face of sulphur ions, so that each tin
atom is bonded to three sulphur atoms only. In this polar arrangement the
tin atoms can be considered to have a tetrahedral environment in which a
lone-pair of electrons occupies one vertex. The cations are ordered so that
barium layers alternate with layers of tin atoms in the overall sodium-chloridetype structure. The crystal structure of gallium thiophosphate, GaPS,, has
been
The compound crystallizes in the monoclinic space group
P2,/c, with the cell constants a = 8.603, b = 7.778, c = 11.858 A; =
135.46'. The structure consists of puckered hexagonally close-packed layers
of sulphur atoms with only the alternate interlayers occupied by gallium and
phosphorus cations. Filled and empty interlayers thus alternate, giving perfect
cleavability parallel to the 100 plane. Gallium and phosphorus atoms are
each surrounded by four sulphur atoms at the corners of a distorted tetrahedron. Bond lengths were found in the ranges Ga-S 2.266 to 2.297 A,
P-S 2.044 to 2.059 A. The sulphur ion seems to be polarized by both cations,
but especiallyby the phosphorus ion. Optimum conditions for the preparation
of the compound AgAsS, in the form of monoclinic single crystals have been
Crystals were obtained by heating stoicheiometric quantities of
silver, arsenic, and sulphur in evacuated quartz ampoules to form a melt at
95O-98O0C. Crystallization was achieved by slow cooling in a thermal
gradient of between 6 and 14' C mrn-l. Some physicochemical properties of
phases based on the compounds KSbS,, RbSbS,, and CsSbS, in the glassy
state have been in~estigated.,~~
Magnetic susceptibility measurements were
used to show that the covalent character of the bonds in these phases increased in the order KSbS, < RbSbS2 < CsSbS,. The ternary sulphides
J. E. Iglesias and H. Steinfink, Acta Cryst., 1973, B29, 1480.
163 M. I. Golovei, A. V. Bogdanova, and E. E. Semvad, Izvest. V. U.2. Khim. i khim.
Tekhnol., 1973,16, 832.
lea Z. U. Borisova, I. V. Viktorovskii, Ya. G. Finkelshtein, S. I. Berul, and N. P. Luzhnaya, Izvest. Akud. Nauk. S.S.S.R., Neorg Materialy, 1973, 9 , 557.
16*

588
Cs2Pt,S, and Rb2Pt3S, have been prepared165by fusion reactions of alkalimetal sulphides, or carbonates, with platinum and sulphur. X-Ray studies on
single crystals show a layer structure of a type similar to that of the monoclinic compound Cs2Pd3Sp,in which the planar sulphur co-ordinations of the
platinum atoms are connected in two dimensions. Rubidium and caesium
carbonates have been shown16sto react at 900 "Cwith Ln203(Ln = La to Tb)
in an atmosphere of H2S to give compounds of the type MLnS, (M = Rb,
Ln = La-Tb; and M = Cs, Ln = La or Ce). Only binary compounds were
obtained with the heavier lanthanide elements.The ternary compounds possess
the a-NaFe02 type of structure. The crystal structures of two further polytypic forms of
and Zn21n2S~68
have been described.
Polysulphide Ions.-Spectroscopic investigations into solutions of alkalimetal polysulphides in DMF have shown169that the formal oxidation state
of the species giving rise to the intense blue colour of these solutions is -8.
Since the actual charge was found to be half that of a polysulphide ion, the
species was identified as the supersulphide ion, Sr. In low-temperature systems (DMF, DMSO) the formation of S? is largely prevented by its tendency
to dimerize to higher polysulphide ions. At elevated temperatures, however,
these long-chain molecules can be expected to become less stable, thus
favouring the shorter ions Sc in equilibrium with S2- (monosulphide), S",(disulphide), :S (supersulphide), and sulphur vapour. A second study,170
by quantitative spectrometric titration, of solutions of Na2S4in DMF, with
milligram portions of sulphur, with absolute exclusion of oxygen, has been
used to explain the assignment of colour and charge of the solutions. In this
study the blue colour is attributed to the S; ion, the red to the Si- ion, and
yellow coloration to the S2- ion:
s,
4s;
s,- 4 s,-
+ 2s; + s;-
All the possible X-ray emission spectra from sulphur in the disulphide ion of
FeS, have been rec0rded.l" These are the K,,,, (2P3/2,1/2--+ 1S1,2), Ks
1s1/2>, and L 2 , 3 (305/2.3/2and3sl/,
2P3/a,,/2).Thesu1phur
(3p3/2.1/2
doublet in Sg- is shifted to longer wavelengths by -0.05 eV in comparison with the element (S8). In order to interpret the data a qualitative
MO diagram was constructed. The 3s orbitals are seen to be essentially nonbonding, in accordance with other indirect arguments concerning the bonding
potential of these orbitals. The bonding in the anion is mostly 3p in character
0. Gunther and W. Bronger, J. Less-Common Metals, 1973, 31, 255.
W. Bronger, R. Elter, E. Maus, and T. Schnitt, Rev. Chim. mint?rale, 1972, 10, 147,
16' F. G. Donika, S. I. Radautsan, S. A. Semiletov, G. A. Kiosse, and I. G. Mustya,
168 F. G. Donika, S. I. Radautsan, S. A. Semiletov, T. V. Donika, and I. G. Mustya,
169 W. F. Giggenbach, J.C.S. Dalton, 1973, 729.
170 F. Steel and H. J. Guttler, Angew. Chem. Internat. Edn., 1973, 12, 420.
171 G. Wiech, W. Kopper, and D. S . Urch, Znorg. Chim. Acta, 1972, 6 , 376.
165
589
in both the 0- and r-bonds but some 3d-orbital participation is indicated.
When water containing sulphide ions is exposed to air, a reaction between the
S- ions and oxygen is
to take place slowly, with the formation of
polysulphides as intermediates. Chronopotentiometric and spectrophotometric examinations at 4O0-42O0C of solutions of sulphur anions in a
LiCl-KCl melt have shown173that S2- is oxidized to the ions Sz- and soluble
S;, the latter ion giving the solution a blue appearance. Quarter-wave
potentials have been measured for the reactions:
S*-
4 S-
S:-
S,
+ e+ 2e-
S;
S+
+ S,-l + 2e-
The spectral maxima at 320, 390, and 590 nm were found to correspond to
absorptions by the ions S2-, S",-, and S;, respectively. Direct observations
(resonance Raman, i.r., and e m . spectra) and indirect measurements
(visible-u.v. spectra, conductivity, and magnetic susceptibility) strongly
suggest1'* that the intensely blue species formed by alkali-metal polysulphides
or elemental sulphur in hexamethylphosphoramide can be attributed to the
S, radical anion. Cryoscopic, conductance, and magnetic measurements and
i.r. and U.V. spectral data have been used175to study the cations formed in
solutions of sulphur in disulphuric acid. The blue coloration was shown to be
due to the formation of the Si+ ion and the colourless solutions were found
to contain the Si- ion. The solid compounds S4S3OI0and SsS3Ol0,formed by
the action of SO, on elemental sulphur in SO2 media at low temperatures,
have been isolated and characterized.
Hydrogen Sulphide.-The differences in the proton affiities of H2S and H 2 0
have been measured in a photoionization mass spectrometer by studying176
the equilibrium:
HsStg,
+ H20W f
H,O;C,,
+ H2Sus,
Mixtures of H2Sand H 2 0are photolysed at 10.63 eV in the source of the mass

spectrometer. H2S+, which is the only ion produced, reacts with H,S to give
H3S+. This ion reacts with H 2 0 to produce H30+, which further hydrates to
H(H,O)$. The proton affinity of H,S was found to be some 3 kcal mol-l
greater than that of H,O. The electron-impact-induced ionization and dissociation of H 2 0 and H2S have been studied177using a quadrupole mass
spectrometer, and a comparison has been made with the corresponding
photoionization and photoelectron spectra. 1.r. studies178on the adsorption
ln
173
174
176
178
17'
178
K. Y.Chen and S. K. Gupta, Environ. Letters, 1973, 4, 187.

J. P. Bernard, A. Dettaan, and H. Van der Poorten, Compt. rend., 1973, 276, C, 587.
T. Chivers and I. Drummond, Znorg. Chern., 1972, 11, 2528.
K. C. Malhotra and J. K. Puri, Indian J. Chem., 1972, 10, 734.
J. M. Hopkins and L. I. Bone, J . Chem. Phys., 1973, 58, 1473.
J. D. Morrison and J. C. Trheger, Znternat. J. Mass Spectrometry Zon Phys., 1973, 11,
77.
T. L. Slager and C. H. Amberg, Canud. J. Chem., 1972, 50, 3416.

and subsequent reaction of H2S on alumina showed major bands at 1341,
1568, 1625, and 3400 cm-l. Relative band intensities were used to follow the
first-order decomposition of the adsorbed H2S and the formation of H20. A
mechanism consistent with the spectral and kinetic data suggests adsorption
on to an exposed aluminium ion to form an AI-S surface bond and hydrogenbonding to neighbouring 0 and OH species. The effect of other gases on the
radiation yield of hydrogen from the a- and y-radiolysis of H2S has been
HCl was found to increase the yield of hydrogen, whilst CS2
lowers the yield. The theoretical maximum temperature of a hydrogen sulphide-fluorine flame has been calculated1R0as 3469K by assuming an
equilibrium:
590
HZS
+ Fz + 2HF + S
The reaction between hydrogen atoms and H,S, with and without added NO,
has been studiedlS1by following the H atom, S atom, and SH radical concentrations with time, by e.s.r. techniques. The results of the study may be
fully explained by the mechanism:
+ HZS H, + SH
+ SH H, + S
S H + NO -+ stable species
SH + SH + HZS + S
H
H
The action of H,S on boron halides (other than BF,) has been shownlS2to
yield the new substitution products BX2SH, BX(SH),, and B(SH),, along
with the corresponding hydrogen halide. These halogenosulphydroboranes
are unstable and cyclize to the cyclic boron sulphides (BSSH), or (BSX),. In
the case of BBr, it was possible, by controlling the ratio of reactants and
temperature, to promote the formation of one of the three possible substitution products and then, by encouraging cyclization, to obtain, rapidly and
selectively, either (BSSH), or (BSBr),. The synthesis of (BSCl), was accomplished by the dissolution of (BSSH), in liquid BCl,, and (BSI), by the
action of H2S on solid BI,. During a studylR3of the catalytic oxidation of
H,S over carbon, it was noticed that a large amount of mercury (from the
monometers and pump) was taken up by the sulphurized carbon catalyst at
140 'C. Since the physical adsorption of mercury at this temperature is small,
it is suggested that the sulphur in the carbon is reacting with the mercury to
form mercuric sulphide. The Schroeder-Lippincott potential-function model
of the hydrogen bond has been usedla4to study the properties of hydrogenbonded sulphur systems. The model predicts comparable intermolecular bond
179
180
182
lS3
D. W. Huyton and T. W. Woodward, J.C.S. Faraday I, 1973, 69, 1049.

J. Chevaleyre, C. Matray, and J. Janin, Spectrochim. Acta, 1973, 29A, 1091.
J. N. Bradley, S. P. Trueman, D. A. Whytock, and T. A. Zaleski, J.C.S. Faraduy I,
1973, 69,416.
J. Bouix and R. Hillel, Canad. J. Chem., 1973, 51, 292.
R. K. Sinha and P. L. Walker, Carbon, 1972, 10, 754.
W. R. Snyder, H. C. Schreiber, and J. N. Spencer, Spectrochim. Acta, 1973, 29A,
1225.
591
strengths and frequency shifts for 0-H- - SO and 0-H- - -S, although
intrarnolecularly bonded 0-H- - -S bond strengths and frequency shifts will
be larger than those of 0-H- - -0,S-H. - -0,
and S-H- - -S; inter- and
intra-hydrogen bonds are weaker than 0-H- - S, but intramolecular
S-H. * 00bonds are comparable in bond strength to 0-H- - -0intramolecular bonds.
Sulphur-Halogen Compounds.-The reaction of gaseous SF, with carbon in a

heated Knudsen cell has been studiedls5by mass spectrometry, and several
new molecular species, including SF, SF,, and SCF,, have been identified.
Ionization potentials, with an estimated accuracy of 0.10 eV, have been obtained and AH; for the process:
SF, 3 SFo
+ 2F
and AHfo298 for SF, have been derived. The following standard heats of formation were also derived: SF 2.2, SF2 -71.4, and SCF, -75.0 kcal mol-l.
The photoelectron spectra of the isomeric difluorides FSSF and SSF, have
been examined.ls6Only slight differences were observed. High yields of pure
SF, have been reported18' from the fluorination of elemental sulphur in
CC1,F at -78 "C. The X-ray photoelectron spectrum of SF, clearly showsls8
the resolution of the two peaks for the 1s electrons of the fluorine atoms. This
confirms the existence of equal numbers of the non-equivalent fluorine atoms
in this molecule. Fluorine (l8F)exchange has been observed189between Group
I metal fluorides and SF, at 150 and 50 "C. Chlorine (,,Cl) exchange between
Cl, and SF,CI at 150 "C was found to be enhanced by the presence of Group 1
fluorides. The e.s.r. spectra, observed during the photolysis of certain peroxides and hypofluorites containing dissolved SF,, have been ascribedlgOto
radicals of the type XSF, (X = F, CF,O, or SF,O), in which the unpaired
electron and bonding orbitals are distributed octahedrally about the sulphur
atom. The first examples of the formation and identification of both the cisand trans-isomers of R1SF,R2 (R1 = CF,, R2 = CF, or C,F5) have been
reported.lgl
The experimental results for the laser-induced fluorescence of SF, and
SF,-rare gas mixtures have been reported.lg2 The interaction of SF, with
metals and oxides has been studiedlg3by thermal analysis techniques. It was
shown that SF, is an active fluorinating agent, reacting with oxides at temperatures between 600 and 700 "C and with metals between 500 and 600 "C.
la6
D. L. Hildebrand, J. Phys. Chem., 1973,77, 897.
lS6
G.Wagner, H. Bock, R. Budenz, and F. Seel, Chem. Ber., 1973, 106, 1285.
D. Naumann and D. K. Padma, Z . anorg. Chem., 1973, 401, 53.

R.W.Shaw, T. X. Carroll, and T. D. Thomas, J. Amer. Chem. SOC.,1973, 95, 2033.
lS0 C.Joy, W.Fraser, D. W. A. Sharp, G. Webb, and J. M. Winfield, J.C.S. Dalton, 1972,
2226.
loo J. R. Morton and K. F. Preston, Chem. Phys. Letters, 1973,18, 98.
lol T. Abe and J. M. Shreeve, Inorg. Nuclear Chem. Letters, 1973,9, 465.
lS2 R. D.Bates, J. T. Knudston, and G. W. Flynn, J. Chem. Phys., 1972,57,4174.
lQ3 A. A. Opalovsky and E. U. Robkov, J . Fluorine Chem., 1973,2,349.
la*
592
Oxides were generally converted into fluorides whilst metals gave both
fluorides and sulphides.
The crystal structure of trifluorosulphur(1v)yl tetrafluoroborate,
[SF,]+[BF,]-, has been determined.lg4The compound is orthorhombic, with
a = 9.599, b = 5.755, c = 8.974 A; 2 = 4; space group Pnma. The structure
consists of discrete SF, and BF, groups. The SF, group has site symmetry
C, with interatomic distances S-F(l) = 1.495 and S-F(2) = 1.499 A and
bond angles F(l)SF(l) 97.62' and F(2)SF(1) 97.39', and effectively C,,
symmetry. Each SF, group is so orientated that the sulphur atom makes short
contacts of 2.624 (twice) and 2.593 A with fluorine atoms of the three closest
BF, groups. Each sulphur atom is in a trigonally distorted octahedral environment of fluorine atoms. The bond length in the cation (Figure 3) is the shortest
F1
Figure 3 i%e shape of the [SF# ion in [SF3]+[BF4](Reproduced by permission from Inorg. Chem., 1972,11,2328)
yet observed in any sulphur fluoride and is some 0.07A shorter than the
P-F bond in PF,.
The compound [SF,]+[AsF,]- is also orthorhombic with the arsenic and
sulphur atoms in a nickel arsenide lattice, with each sulphur lying approximately at the centre of a trigonal prism defined by arsenic atoms. The reaction
of FC(0)N: SF, with AsF,, in excess, at -80 O C has been shownlg5to give
[SF,(NcO)]+[AsF,]-. The reaction of FC(0)N: SCl, with AsF, in excess, at
room temperature, gave [SCl,(NCO)]+ [AsF,]-.
A new species, the chlorodisulphanyl radical (ClSS'), has been producedlg6
by the photolysis of Cl,S, in inert matrices at 4.2 K. The identification of the
species rested on the complete simulation of its well-resolved e.s.r. spectrum.
Equimolar amounts of SCI, and S,C12 have been shownlg7to react with
phenylperthiophosphonic anhydride (13) to yield, quantitatively, bis(pheny1chlorothiophosphory1)-tri- (14) and -tetra-sulphane (13, respectively, The
D. D. Gibler, C. J. Adams, M. Fischer, A. Zalkin, and N. Bartlett, Inorg. Chem., 1972
11,2325.
lB5
R. Mews, Z. Naturforsch., 1973, 28b, 99.
lg6 F. G. Herring, C. A. McDowell, and J. C. Tait, J . Chem. Phys., 1972, 57, 4564.
lg7 E. Fluck, F. Ibanez, and H. Binder. Z.anorg. Chern., 1973,397, 147.
lo4
s s
Ph-PI
/I1
P-Ph
+ SCl2
593
S
II
i
Ph-P-S-&S-P-Ph
c1
II
I
c1
(PhPS2)2
SOzClz-
Ph-P-L-PP-Ph
CI
II
1
CI
SO2
(16)
S
(PhPS&
SOCl2
II
Ph-P--P-S-S-P-Ph
c1
I
i
&I
(17)
corresponding disulphane (16) is the primary product of the reaction between

(13) and S02C12,whilst (13) and SOCl, yield the compound (17).
Sulphur-oxygen-Halogen Compounds.-The crystal chemistry of the halogen-sulphur bond has been studiedlQ8in the complex Pt(Me)(PPhd,I,SO,,
which may be crystallized from benzene solutions of the complex, saturated
with SO2.The iodine atom forms a weak bond to sulphur (3.591 A), which is
shorter than the sum of the van der Waals radii (3.80w), although much
longer than expected for a single covalent bond (2.37 A). The angle OSO was
found to be 116.1. The adduct was shown to be similar to adducts of SOz
with metal complexes and amines, and is also a good model for SO2solvates
of halide salts, none of which have been structurally characterized. The
liquid-phase Raman spectra of bis(pentafluorosu1phur) peroxide SF,00SF5
and (pentafluorosu1phur)fluorosulphuryl peroxide SF,OOSO,F have been
reportedlg9 in the region 2000-100 cm-l, and the previously reported i.r.
data have been extended down to 400 cm-l. Assignments for the normal modes
of vibration were made on the basis of staggered, non-planar structures,
similar to that of H202.The 0-0 stretching frequencies were found at 751
and 740 cm-l for SF,00SF5 and SF,OOSO,F, respectively; these unexpectedly low values were attributed to extensive vibrational coupling.
lo8M.
looH.
R.Snow and J. A Ibess, Inorg. Chem., 1973, 12, 224.

A. Carter and J. M. Shreeve, Spectrochim. Acta, 1973, 29A, 1321.
594

06
Figure 4 The molecular structure of S205F2,with Jinal estimated parameters

(Reproduced by permission from Canad J. Chem., 1973, 51, 2047.)
The preparation of pentafluorosulphur hydroperoxide F5SOOH by the

reaction :
F,SOOC(O)F 4- HaO -+ FSSOOH
+ C 0 2 + HF
has been reported.200The compound, which is a stable colourless liquid up to

30 "C and freezes at -55.6 "C, may be used as a convenient source of the
F,SOO group in synthesis. The molecular structures of S20,F, and S,08F2
(Figures 4 and 5 ) have been determined201in the vapour phase by electron
diffraction. In each case it was assumed that a single rotamer was more stable
than all others by at least 2.5 kcal mol-l.
The adduct CsF,SF,O has been prepared202and characterized by i.r. and
013
Figure 5 The molecular structure of S308F2,with final estimated parameters.

(Reproduced by permission from Canad J. Chem., 1973,51,2047)
201
202
D. D . DesMarteau, J . Amer. Chem SOC.,1972,94, 8933.

J. L. Hencher and S. H. Bauer, Cunud. J. Chem., 1973, 51, 2047.
K. 0. Christe, C. J. Schack, D. Pilipovich, E. C. Curtis, and W. Sawodny, Inorg.
Chem., 1973, 12,620.
595
Raman spectroscopy. All eleven fundamental vibrations expected for a
pseudo-octahedral anion (1 8) of symmetry C,, were observed and assigned.
F
(18)
A modified valence force field was computed for the ion SF50-, which
showed a value of the SO stretching force constant lower than those found for
S=O double bonds and suggested an SO bond order of about 1.5. Likewise,
low values were found for S-F stretching force constants, thus indicating
significant ionic contributions to the SF bonds in SF50-. These results were
therefore interpreted in terms of the resonance structures (19) and (20).
\A/
:ij:
:0:
F
etc.
F'PF
F
(19)
F / \F
F(20)
A study203of the iodine-peroxydisulphuryl difluoride system has confirmed

the existence of the previously known solid compounds I(SO,F),, ISO,F, and
I,SO,F. A new compound I,S03F, of melting point 90.5 "C, was also established and the complete phase diagram for the system was determined from
melting-point data. High viscosity over most of the range of composition
indicated polymerization in the liquid state. The i.r. and Raman spectra of
polycrystalline S0,C12 indicate204that the primitive cell contains more than
four molecules, most likely located on general positions. Further, the crystal
is non-centrosymmetric and belongs to either the orthorhombic, tetragonal,
or hexagonal systems. The intensity of the S-0 band of SOCI, increases
markedly205with increasing dilution of a 10 volume% solution in CC14,
SiCl,, and GeCl,. The systems do not form SO-MCI, donor-acceptor bonds,
the change in intensity being ascribed to a change in the short-range order of
the solutions. The photoelectron spectra of some sulphuryl and thionyl
halides have been measured?O6 The sulphur-oxygen bond order was found to
decrease in the order S02F2> SOF2 > SO,Cl2 > SOCI,, and a consideration
of the average ionization energies for w-orbitals involving the oxygen atom
*04
*06
*Os
C. Chung and G . H. Cady, Inorg. Chem., 1972,11,2528.

J. Tremblay, C. Nolin, and R. Savoie, Canad. J . Chem., 1973, 18, 36.
T. N. Naumova, T. S. Uvedenskaya, and B. D. Stepin, 2hur.fiz. Khim., 1973,47,720.
D. Chadwick, D. C. Frost, F. G. Herring, A. Katrib, C. A. McDowell, and R. A. N.
McLean, Canad. J. Chem., 1973,51, 1893.
39
596
showed S02F2w SOF, > SO,Cl, > SOCI,. From an e.s.r. study207of radicals
present in y-irradiated sulphuryl chloride at 77 K it was concluded that the
species present is probably the S0,Cly radical. The unpaired electron is
primarily (76 %) on the sulphur atom with a very high 3s character and on the
two equivalent chlorine atoms with a high 3p character. A single-crystal e.s.r.
study on the S0,ClZ radical anion has shown20sa C,,trigonal-bipyramidal
structure.
Sulphur-Nitrogen Compounds.-The chemistry of sulphur-nitrogen compounds has been reviewed.,09 In particular, the newer aspects of these compounds were related to a background of earlier work and attention was drawn
to structural similarities between certain recently discovered compounds and
elemental sulphur. The topics covered include S4N4and its reactions with
Lewis acids, thionitrosyl derivatives, imide derivatives, and anionic and
cationic species.
Linear Compounds. An electron-diffraction study210 of gaseous thiazyl

chloride has shown the molecule to have the arrangement NSCl rather than
SNCl. This result is in agreement with recent microwave studies on the
Figure 6 The structure of bis(dQhenylmethylene)S3N4

(Reproduced from J.C.S. Chem. Cornm., 1973, 36)
molecule. The fluorine atoms of the NSF2 group in sulphur difluoride NN-perhalogenoalkylimideshave been shown211to be readily exchanged using
R,NSiMe,, RN[SiMe3],, or RONa to give compounds of the general formulae
RhalN=S(OR)2, R,,,N=S(OR)F, R,,,N=S=NR,
RhalN=S(NR2),, and
R,,N=S(NR,)F
(R = Me or Et; Rhal = CF,ClCF, or CFCl,CF,). In the
interaction of sulphur dichloride imides with N-silylated secondary amines,
monochlorosulphur imides RhslN=S(NR2)Cl are formed. These compounds
show physical and chemical relationships to analogous compounds in the
O=S(X)Y system. In crystalline form bis(diphenylmethylene)S,N, exists212
as a chain structure (Figure 6 ) , with the central five members of the S-N
chain coplanar. The crystal is orthorhombic, of space group Pcan. The
207
208
2os
212
K. V. S. Rao and M. C. R. Symons, J.C.S. Dalton, 1973, 9.

T. Gillbro and F. Williams, Chem. Phys. Letters, 1973, 20, 436.
H. J. Emeleus, Endeavour, 1973, 32, 76.
W. C. Emken and K. Hedberg, J. Chem. Phys., 1973, 58, 2195.
R. Mews and 0. Glemser, Inorg. Chem., 1972, 11, 2521.
E. M. Holt and S . L. Holt, J.C.S. G e m . Comm., 1973, 36.
597
structure shows the central sulphur atom of the molecule, lying on an axis
of two-fold symmetry, the angle at this sulphur atom being 123.8' compared
with the angle of 100" usually found. Although the central five members of the
S-N chain are planar, the remaining nitrogen atoms are 0.49 A from the
plane. This is surprising when one considers the possible further delocalization
of the a-bonding that would result from full planarity.
The cryst a1 and molecular structure of 1,5 -bis-(p-chloropheny1)-2,4-diaza1,3,S-trithiapenta-2,3-diene,obtained from the reaction of p-chlorophenylmagnesium bromide with S4N4,has been determined.213The crystals are
monoclinic,ofspacegroupP2,/c,Z= 4 , a = 3.972,b = 19.531,~= 19.37 A,
= 109.7'. The nearly planar structure of the molecule (21) is of the linear
Ar-S-N
vN-s2-Ar
(21)
thiodi-imide type, with cis-cis geometry around the central N2S unit. The
outer nitrogen-sulphur bonds average 1.660 and 1.550 A, respectively. The
sulphur(Sl)-sulphur(S2) distance of 3.293 A is clearly incompatible with the
values expected for a covalent bond (2.05-2.10 A). It is, however, somewhat
below the sum of the van der Waals radii for two sulphur atoms. SS-Dimethyl
sulphurdi-imide, Me,S(NH),, reacts214 with tin chlorides of the type
Me,SnCI,,,)
(n = 0, 1,2, or 3) to form 1 :1 complexes of the general formula
Me,S(NH),,SnMe,Cl+,).
Transamidation of tin dialkylamides with
Me,S(NH), yielded NN-bis(trimethylstanny1)-SS-dimethylsulphurdi-imide
(22) and the polymeric compounds (23) and (24).
II
Me-%Me
Me-!&Me
II
I
21s
F. P. Olsen and J. C. Barrick, Inorg. Chem., 1973, 12, 1353.
214
D. Hanssgen and R. Appel, Chem. Ber. 1972, 105, 3271.
598
A dynamic n.m.r. investigation215of several bis(amino)sulphides (R,N),Sn,

where R = Me, Et, or Pr' and n = 1 or 2, has been carried out in order to
gain stereochemical information for these compounds. The lH n.m.r. spectra
of (Et,N),S and of the di-isopropylamino-derivativewere found to be
temperature-dependent. The low-temperature spectra were thought to indicate a conformation in which the R groups bonded to a planar (or rapidly
inverting) nitrogen remain equivalent as S-N rotation slows. The only
reasonable configuration which satisfied this criterion was one in which the
two NR2 planes are perpendicular to the SN2 plane (25). The bis(amino)
disulphides were thought to be more complex, and the data were explained
by either of two structures (26) and (27). Whilst no discrimination could be
made between these structures, it was thought that (27) may be the most
reasonable since the conformation about the S-N bond is identical with that
of (25).
The reaction of trichloromethanesulphenyl chloride with ammonia at
216
V. W. Hu, J. W. Gilje, and T.T. Bopp, Inorg. Chern., 1973,12,955.
599
-70 C in n-pentane has been shown216 to give trichloromethanesulphenamide :

ClaCSCl
2NHS + ClaCSNH2 + NHaCl
Bis(trifluoromethylsulphenyl)amine, (F,CS),NH, is a very weak acid and

interacts with trimethylamine (and pyridine) to form 1:1 adducts :
(FaCS)aNH
+ NMe,
4 (F,CS),,NMe,
Ring Compounds. The reaction of S4N4with two moles of (MejSn),N has

been shown217 to yield 5 $dimethyl- 1,3A4,2,4,5-dithiadiazastannole (28),
sulphur NN-bis(trimethylstanny1)di-imide (29), and tetramethylstannane.
According to i.r. investigations, the first reaction products are only (29) and
sulphur. Me4Sn and (28) are formed on vacuum-sublimation of the primary
S4N4 + 2(MesSn)~N
Me
\Sn/-I
I \
Me
+ 2Me3Sn--N=S=N-SnMes
+ Me4Sn
N=S
products. Nucleophilic attack of the sulphur on one tin atom of (29) then
leads to ring closure with migration of a methyl group. The yellow compound
(28) is solid at room temperature, but decomposes at 198 OC and may be
recrystallized from CH2CI2.It was characterized by elemental analysis and by
its mass spectrum. Molecular weight determinations indicated the formation of
a dimer in solution with the proposed structure (30).
The crystal structure of the compound N3S3F3has been determined218
from single-crystal X-ray data. The molecule forms a slightly puckered sixmembered (S-N), ring with axial fluorine atoms. In contrast to the compound S4N4Fthe molecule contains no alternating single and double bonds
in the ring. The sulphur-nitrogen bond lengths were found to be 1.587 and
1.598 A, and the sulphur-fluorine bond lengths 1.610 A. The heats of fusion
216
217
21a
A. Haas and R. Lorenz, Chem. Ber., 1972,105, 3161.

H. Roesky and H. Weizer, Angew. Chern. Internat. Edn., 1973, 12, 674.
3. Krebs and S . Pohl, Chern. Ber., 1973, 106, 1069.
600

of Q-(SNOC~)~,
S3N303Cl(C,H,),, (SNOF),, and S3N303F(C,H,), and the
heat of decomposition of cc-(SNOCl)3have been determined.219
The geometries of S4N4and Si+ have been rationalized220by treating each
species as a flexible eight a-bonded framework with sulphur atoms defining
corners of a polyhedron compatible with the number of available higherenergy delocalized electron-pairs. The approach assumes that (a) many
unsaturated flat or cluster compounds can, at a simple level, be regarded as
being composed of a a-bonded molecular framework with a superimposed set
of higher energy electron-pairs in relatively delocalized molecular orbitals ;
(b) two-co-ordinate sulphur consistently provides two electrons for the abonds and one of the two lone-pairs on each sulphur atom interacts with
empty sulphur d-orbitals to give, as in the Huckel species S2N2,SaN8, and
S,N$, two further bonding electrons of higher energy; (c) the a-framework is
flexible and will tend to adopt a shape such that the maximum number of
constituent atoms occupy corner positions of a polyhedron of shape compatible with the number of higher energy bond pairs and the number and
symmetry of the available atomic orbitals not involved in the a-framework.
The crystal structure of the compound S,(NMe)4 has shown221the eightmembered ring to have the crown configuration (Figure 7), with approximate
C(1)
Figure 7 Bond lengths and angles in S4(NMe)4;standard deviationsfor S-N,

N - C , LNSN, L S N S , LSNC are 0.009, 0.015A,and 0.4, 0.6,
0.8', respectively
(Reproduced by permission from Canad. J. Chem., 1973,51,2504)
219
220
821
R. L. McKenney and N. R.Fetter, J. Inorg. Nuclear Chem., 1972, 34, 3569.

A. J. Banister, Nature Phys. Sci.,1972, 239, 69.
A. L. MacDonald and J. Trotter, Canad. J. Chem., 1973, 51,2504.
601
C,, symmetry, and the bonds at each nitrogen atom are slightly but significantly non-planar. Mean bond lengths are S-N 1.677, C-N 1.479 A.
Molecular 1:1 adducts have been prepared222between S4N4and AICI,. 1.r.
spectra of the compound S4N4,AIC13and those of S4N4,SbC15and S,N,,BF,
suggest an analogous structure. The compound S4N4,AIC13also resembles the
compound S,N,,BCl, in adding a further mole of SbCl, to yield
S4N4,AICI, ,S bCI,.
Silicon-nitrogen (and tin-nitrogen) compounds of the type Me3SiNR2,
where R = Me or Et, when treated with S4N4in the molar ratio 2: 1 have been
to yield products containing an S2N3 skeleton:
2Me,SiNR2
+ S,N,
---+
2Me3SiN=S==N-SNR2
The reaction appears to involve the nucleophilic attack by the amino-nitrogen

on a sulphur atom of the S4N4ring, leading to electrophilic cleavage of the
metal-nitrogen bond (3 1).
Trichlorocyclotrithiazene, the cyclic trimer of thiazyl chloride, NSCl, is

commonly prepared by the action of chlorine on S4N4or S3N,Cl2. An alternative preparation has been described224involving the action of sulphuryl
chloride on S4N4or chlorocyclotrithiadiazonium chloride, S,N,Cl+Cl-. The
method is said to be more convenient and to yield a purer product.
The synthesis of the first oxide of the S4N4ring has been described.225
NN-Bis(trimethylsily1)sulphur di-imide reacts with the anhydride of fluorosulphuric acid with cleavage of trimethylfluorosilane and trimethylsilyl
fluorosulphate to give s,&o4 (32). The compound is a yellow solid which
+ 2FSO2--0-SO2F
2Me3Si-N=S=N-SiMe3
222
223
224
225
C. H. Chan and F. P. Olsen, Znorg. Chem., 1972, 11, 2836.

H. W. Roesky and M. Dietl, Angew. Chem. Internat. Edn., 1973, 12, 424.
G . G.Alange, A. J. Banister, and B. Bell, J.C.S. Dalton, 1972, 2399.
H. W. Roesky and 0. Peterson, Angew. Chem. Internat. Edn., 1972, 11, 918.
602
sublimes at 80-90 "Cunder vacuum and decomposes between 1 15 and 120 'C.
In the presence of moisture the compound decomposes with loss of SO2and
turns brown.
The crystal and molecular structure of the novel compound NH4[S4N50]
has been determined.226The compound crystallizes in the monoclinic space
group Q/m, with a = 17.848,b = 6.232, c = 7.095 A; @ = 104.83O;2 = 4.
One hydrogen atom of the NH; ion is bound to the oxygen atom of the anion
and two hydrogen atoms are bound to the nitrogen atoms of two further
anions. Thus only one of the four hydrogen atoms of NHa does not take part
in a hydrogen bridge and the cation is therefore strongly deformed. The
structure of the anion (33) can be formally derived from the cage of S4N4,
(33)
one S atom carrying an 0 atom and being bridged to a neighbouring S atom

through an N atom. The oxidized sulphur atom is almost tetrahedrally coordinated. The S-N bond distances are somewhat more strongly differentiated than in S4N4;nevertheless it is assumed that largely delocalized n-bonds
exist within the S4N, skeleton. The formation of (S,N,O)NH, from SOCl,
and NH3 may be interpreted as a series of successive condensations with
elimination of HCl, H20, and NH3:
+ 7NH, "s, HN(SONH2)%+ 4NH4C1

Z
NH4[S4N60] + 3H20
2HN(SONH2)2H
2SOC1,
A refinement227of the crystal structure of S6(NH)2I1 has shown that the

average bond length of the S-N bonds (1A80 A) is approximately equal to
the lengths found in S,(NH), I11 (1.672 A) but smaller than the value observed in S6(NH), I (1.724). As observed for other compounds with the
formula S,-,(NH),, the molecules in S6(NH), have the crown conformation.
Heptasulphur imide may be2,* completely deprotonated by treatment of
its solution in THF with powdered KOH at -62 ' C . The resulting solution
226
227
2a8
R. Steudel, P. Luger, and H. Bradaczek, Angew. Chem. Internat. Edn., 1973,12, 316.
H. J. Postma, F. Van Bolhuis, and A. Vos, Acta Cryst., 1973, B29, 915.
M. H. Mendelsohn and W. L. Jolly, J. Inorg. Nuclear Chem., 1973, 35,95.
603
of K+S,N- reacts with Me1 to give an essentially quantitative yield of the
N-methyl derivative of the heptasulphide imide. Extended treatment of
K+S,N- solution with KOH causes irreversible decomposition. In solution,
the S,N- ion undergoes spontaneous isomerization, probably to an openchain form; at temperatures above -4OOC the rate of isomerization is
sufficientto permit equilibrium between the two forms to be readily achieved.
The solid-state reaction between sulphur and ammonium chloride in the
presence of thiourea, as a catalyst, has been shown229to yield a new sulphur
nitride polymer with the composition S,,N,Cl,. The postulated mechanism of
reaction is as follows:
+ 2NHpCl S2CI2 + 2NHs + HIS

2SaCla + 4NHS + 4 s -+ SoN4 + 4HC1 + 4H2S
2S4N4 + Sacla -+ S,oN,CI,
3s
The compound is obtained as a brown powder, melting point >36OoC,

insoluble in water and acids but completely soluble in alkali. On the basis of
i.r. studies the structure of S,,N,Cl, was represented as a resonance between
the two forms (34) and (35).
S-N=S
c1
S-N-S
ls''l
N I N
IA\l
CN=S
S-N-S
I
I
c1
An X-ray crystallographic studyz3, of the a-form of undecasulphur

dinitride (S,,N,) has shown the molecule to consist of two rings, each shaped
like the cyclo-octasulphur ring, fused at the lY3-positionand with the bonds
from nitrogen coplanar (36). Several properties of the molecule have been
namely solubility, polymorphism, enthalpy of formation, and
229
230
231
S. Rajeswari, Indian J. Chem., 1972, 10, 441.

M. S. Shahid, H. G . Neal, and H. Garcia-Fernandez,J. Inorg. Nuclear Chem., 1973,
35, 1693.
H . Garcia-Fernandez, H. G. Neal, and G. Teste de Sagey, Compt. rend., 1972, 275,
C, 324.
604

51
s2
vibrational spectra. The evidence used to show that thep, electrons of the
sulphur are involved in 7-bonding and not present as lone pairs was outlined.
Sulphur-Nitrogen-Phosphorus Compounds.-Thermolysis of compounds of
the type R,PCl=N-SO,X
(R = C1, Me, or Ph; X = F or Cl) has been
to result in the formation of the compounds R2P(0)Cl and
[NS(O)X],. Pyrolysis of phosphorus-sulphur-nitride halides with longer
chains yields, amongst others, the cyclic compounds (37) and (38). The
compound (38) is also one of the decomposition products of the sulphamide

derivative (39). Bicyclic phosphorus trisulphur pentanitride (40) has been
prepared233by the reaction of [Me3SiN],S with PF, at 0 'C.The compound
was characterized by n.m.r., ir., and mass spectra. From n.m.r. data it was
1
C&P=N-P(O)Cla
232
W. Haubold, E. Fluck, and M. Becke-Goehring, Z . anorg. Chern., 1973, 397, 269.

H. W. Roesky and 0.Peterson, Angew. Chem. Internut. Edn., 1973, 12, 415.
605
(40)
concluded that one fluorine atom occupied an equatorial position, the other
an axial position. In the mass spectrum the ion of highest mass number
was the six-membered-ring compound S,N3PF2,formed by cleavage of NSN.
Sulphur-Boron Ring Compounds.-Trimeric metathioboric acid (HSBS), has
been
to be monoclinic in the space group P2,/c, with a = 13.949,
b = 4.133, c = 17.538 A, = 114.76. The molecules (41) form six-membered
rings which are nearly planar. The mean bond distances for cyclic and
S
i
(41)
(42)a;
R = Me
b; R = C1
terminal B-S bonds are 1.803 and 1.813 A, respectively. Dimethyl 1,2,4trithia-3,5-diborolan has been
by electron diffraction, to have an
approximately planar skeleton (42a). The boron-sulphur bond distances are
nearly all equal, with a mean distance of 1.803 A; the S-S bond distance is
2.076A. A similar
of the dichloro-compound (42b) showed an
identical planar configuration, with bond distances very little different from
those of the dimethyl compound.
Sulphur-Oxygen Compounds-Magnetic
susceptibilities have been reported237for a number of compounds containing sulphur-oxygen bonds. The
magnetic susceptibilities of HSO: and SO!- or HS04 and SOP were not very
different, since these species differ only in a proton, and although the extent
of delocalization of the r-electrons must be somewhat different, this evidently
has only a small effect on the susceptibilities. Taking the average values for
the ionic susceptibilities/10-6e.m.u. mol-l in each series, it was found that
the value for S2- = 22.8, SOg- = 28.6, SO:- = 42.45. Thus a rise of only
234
236
236
W. Schwarz, H. D. Hausen, H. Hess, J. Handt, W. Schmelzer, and B. Krebs, Acta

Cryst., 1973, B29, 2029.
H. M. Seip, R. Seip, and W. Siebert, Acta Chem. Scand., 1973, 27, 15.
A. Almenningen, H. M. Seip, and P. Vassborn, Acta Chem. Scand., 1973, 27,21.
M. B. Kennedy, M. W. Lister, R. Marson, and R. B. Poyntz, Canad. J . Chem., 1973,
51, 674.
606
1.93 per oxygen is observed in going from sulphide to sulphite, but there is a
further rise of 11.85 x
e.m.u. mol-l in going to sulphate; this effect was
also noted in the P-0 system.
Crystals of S 8 0 , produced by condensation of SOCl, with crude sulphane
(H,S,, n = 3 , 4 , or 5) and recrystallization from CS,, have been
to
belong to the space groupPca2, witha = 13.197, b = 7.973, andc = 8.096 A.
The molecule S 8 0 belongs to the point group C,; the sulphur atoms form a
crown-shaped ring (43) in which each set of four atoms lies approximately in
one plane, with the two planes almost parallel. The oxygen atom is in an
axial position to the ring, with a sulphur-oxygen distance of 1.483 A, in
agreement with that calculated from valence-force constants. The intramolecular S-S distance shows more pronounced variation than that observed in the s8 ring of rhombic a-sulphur, in particular the two very large
S-S distances involving the thionyl groups (2.20 A). These bonds may best
be regarded as partial bonds, which probably accounts for the ease of
decomposition of S 8 0 to SOz and polymeric sulphur. The microwave spectrum of the molecular transient disulphur monoxide S 2 0 has been reexamined239and microwave measurements have been extended into the
millimetre-wave region. The centrifugal distortion constants, obtained from
the rotational spectrum, have been used to discuss the vibrational spectrum
of the molecule.
Sulphur Dioxide. The X-ray emission and absorption spectra of sulphur in
the SOz molecule have been investigated240both experimentally and theoretically. The spectra are linked energetically, thus making possible an analysis
of the arrangement of occupied and free levels in the molecule. The relative
positions of the energy levels obtained from the X-ray spectra compare
favourably with those obtained by theoretical calculations. The electronic
structures of SOz and SO:- have been investigated2*lwithin the framework
338
23B
240
241
R. Steudel, P. Luger, H. Bradaczek, and M. Rebsch, Angew. Chem. Internat. Edn.,

1973, 12,423.
R. L. Cook, G. Winnewisser, and D. C. Lindsey, J. Mol. Spectroscopy, 1973,46, 276.
L. N. Mazalov, V. M. Berterev, A. P. Sadorskii, and I. I. Guzhavina, J. Struct. Chem.,
1973, 14, 799.
S . P. Dolin and M. E. Dyatkina, J . Struct. Chem., 1973, 14, 838.
607
of a non-empirical variant of the TDOA method. Several papers have been
p ~ b l i s h e d ~on
~ ~experimental
-~~~
and theoretical studies of the i.r. and U.V.
spectra of SO,.
The reduction of SO2 in DMF has been investigated2,' by electrochemical
methods. At a gold electrode, SO2 is reduced by a one-electron process to a
product which when complexed by SO2 is a blue species:
SO3
xso,
+ e-
+ so,
1SO;
1(SO,),SO,
The product also dimerizes to dithionite, S,Oi-, which is also complexed by

SO2, to give a red species:
2s0, -7 s20:-
so2 + s2o:- 1(so,)S,o:The electrical conductances of some 34 electrolytes in liquid SO2 at 25OC
have been measured.248The poisoning of y-alumina by CO, has been shown24g
to suppress the catalytic reaction:
2COS
3
+ SOa + -S,
+ 2C02
X
Using i.r. evidence, a mechanism may be postulated whereby SO2is adsorbed

on hydroxyl sites and COS on aluminium sites on the oxide. The latter sites
become blocked by the irreversible chemisorption of C02. The reaction of
SO, with carbon at elevated temperatures has been shown250to involve the
following reactions :
2c + 230, 3 2c0, + s,
c + s, + CO, 3 2cos
c + 2cos 3 cs, + 2co
c + co, 3 2co
c + s, 3 cs,
The reaction of small amounts of SO,, carried by a nitrogen stream through

of the
an anhydrous CaCO, bed, becomes noticeable above 500 "C. A
formation of the stable compounds suggests the intermediate formation of
CaSO,. Further reaction of CaSO, with SOzyields CaSO, and S,. A secondary
reaction of Sz on CaO (produced by thermal decomposition of CaCO,)
242
243
244
245
246
247
248
24a
250
251
R. J. Corice, K. Fox, and G. D. T. Tejwani, J. Chem. Phys., 1973, 58, 265.

G. D. T. Tejwani, J . Chem. Phys., 1972,57,4676.
V. T. Jones and J. B. Coon, J . MoI. Spectroscopy, 1973, 47, 45.
J. C. D. Brand, V. T. Jones, and C. D. Lauca, J . MoI. Spectroscopy, 1973, 45, 404.
J. C. D. Brand and R. Nanes, J . Mol. Spectroscopy, 1973, 46, 194.
R. P. Martin and D. T. Sawyer, Inorg. Chem., 1972, 11, 2644.
S. Takezawa, Y . Kondo, and N. Tokura, J . Phys. Chem., 1973, 77, 2133.
T. T. Chuang, I. G . Dalla Lana, and C. L. Liu, J.C.S. Fnruduy I, 1973, 69, 643.
J. D. Blackwood and D. J. McCarthy, Austral. J. Chem., 1973, 26, 723.
J. Tarradellas and L. Bonnetain, Bull. Suc. chim. France, 1973, 1903.
608
produces CaS. The reaction of SO2with oxides of the cerium sub-group has
been
to lead to the formation of oxide sulphates of the type
M205S04. During reaction the separation of elemental sulphur was observed; this was thought to be due to a unique disproportionation of the
sulphur ion :
3s4+
+ 2ss+
+ so
The formation of the intermediate complex La203,S0, was proposed, the

complex reacting with a further mole of SO2 to give the final product:
2La203
+ 3so2
+S
2La205S04
Sulphur Trioxide. The He I photoelectron spectrum of SO3 has been measred^^^ and compared with the spectra of SO2and BF,. The results indicate a
substantial stabilization of the sulphur lone-pairs in SO2 and the possible
involvement of central atom d-orbitals in SO3. An anharmonic force-field for
SO3, based on the valence force model, has been investigated.254Gas-phase
Raman and i.r. spectra together with a band-contour calculation have been
to establish beyond doubt the assignment of v2 at 497.5 and v4 at
530.2 cm-l for SO,.
of the kinetics of reactions between oxygen and nitrogen atoms
A
with SO3 has shown that the reaction of oxygen atoms with SO, yields SOz
and O2 as stable products. A white metastable solid condensing at -10 OC
was observed as a probable intermediate. The reactions of SO3 with the
sodium borates Na2B,07 and NaB,O, have been
by chemical, X-ray
diffraction, and thermal analyses. Reaction, which took place between 190
and 200 "C, gave three products:
+
+
+ Na,B,O(S03, + 7(B203,2S03)
2Na2B40,+ 12S03 +- Na2B4(S04), Na2BaO(S04)3 B20s,2S03

4NaB50a
+ %SO3 -+
Na,B,(SO,),
The reactions of SO3 with sodium and barium nitrates are now
to give the compounds KN02S3010 and Ba(N02)2(S,010)2,respectively.
Previously259the reaction was thought to be :
KNO3
+ 7SO3 + K&OIO + (NO2)2S4013
Sulphates.-The structures of sulphates have been discussed260in terms of

two models: (a) the SO4 group is considered to be a large pseudosphere and
A. A. Grizik, N. G. Abdullina, and N. M. Garifdzhanova, Russ. J. Inorg. Chem., 1973,
18, 313.
253 R. L. Dekock and D. R. Lloyd, J.C.S. Dalton, 1973, 526.
2 6 4 A. J. Dorney, A. R. Hoy, and I. M. Mills, J. Mol. Spectroscopy, 1973, 45, 253.
265 A. Kalder, A. G. Maki, A. J. Dorney, andI. M. Mills, J . MoE. Spectroscopy, 1973,45,
247.
256 A. Jacob and C. A. Winkler, J.C.S. Faraday I, 1972, 68, 2077.
257 S. N. Kondrat'ev and S. 1. Melnikova, Russ. J . Inorg. Chem., 1972, 17, 1525.
258 G. Pevergne, P. Legrand, and J. Henbel, Bull. SOC.chim. France, 1972, 4106.
25D H. A. Lehmann and A. Kluge, 2. anorg. Chem., 1951, 265, 120.
2Eo N. L. Smirnova, V. N. Solov'eva, and N. V. Belov, J . Struct. Chem., 1972, 13, 688.
252
609
the structure is built up by the packing of the pseudospheres in relation to the
other atoms in the structure; (b) the oxygen atoms of the SO4group form the
main framework of the structure, the other cations being located in cavities
in this framework. The structure of sulphates has also been considered261in
terms of the types of chains which may be distinguished when the structure is
represented as cation-oxygen polyhedra. Two types of chains are apparent,
consisting of either tetrahedral SO4groups alternating with cation polyhedra
or rods of cation polyhedra to which SO4 tetrahedra are attached. Complex
chain types exist in a number of structures and a classification of the sulphate
chain structures was presented. The angles in nine polysulphate and HS04
ions have been predicted262to within 1.5' using two empirical relationships.
A combination of the bond lengths of the bonds defining the angle, the
configuration of the bonds around the bridging oxygen atom, and the bondstrength relationship made it possible to predict a priori the complete geometry of the S,O;- ion to an accuracy of 0.013 A and 0.8". The variations
in the bond angle may be equally well understood by assuming that they are
caused by 0-0repulsions or by variation in the S-0 bond strengths. The
symmetry of the SO4 ion in gypsum, when considered in isolation, is now
thought263to be a sphenoid in the point group 32rn (tetragonal bisphenoidal),
and not a tetrahedron in the point group 33m as previously
A
new derivative of the SO:- ion, dinitridodioxosulphate(vI),has been identified.26SThe reaction of S02(NH2),with AgN03in concentrated NH40H under
red light and subsequent evaporation gives S02(NHAg),, which, on heating
with excess NaOH at room temperature, gives monosodium trisilver dinitridodioxosulphate(v1) monohydrate (44). Digestion of (44) with an excess of
3SO2(NHAg)Z + 3NaOH
2AgNN,/oNa
9 HzO
AgN@ 'OAg
(44)
+ NaNHSOzNHz
warm aqueous AgNO, gives the insoluble dark-red tetrasilver dinitridodioxosulphate (45). 1.r. spectra indicate tetrahedral symmetry (C2Jfor the SN,Oiion.
The behaviour of several oxoanions (HSOz, HSO,, SO:-, SO:-) dissolved
in molten NaN03-KN03 eutectic at 300 "C has been studied266by means of
L. I. Gorogotskaya and G. B. Bokii, Russ. J. Struct. Chem., 1972, 13, 600.
1. D. Brown, Acta Cryst., 1973,B29, 1979.
2 6 3 W.F. Cole and C. J. Lancucki, Nature Phys. Sci., 1972, 240,48.
2G4 W.F. Cole and C, J. Lancucki, Nature Phys. Sci., 1972,238, 96.
z G 5 E. Nachbaur and A. Popitsch, Angew. Chem. Internat. Edn., 1973, 12, 339.
26* M.Fredericks and R. B. Temple, Austral. J. Chem., 1972,25,2319.
261
2G2
610
AgNNS/oNa,
'OAg
HzO + AgN03
A&
an oxygen electrode. NaHSO, and NaHSO, were found to decompose rapidly

to form S,O;- or S,O;- and water. SO:- and SO:- dissociated to a measurable
extent to form 02-,and the equilibrium constants were determined for the
reactions :
sot- + so* + 0 2 so:- 1so2 + oa-
Under the conditions used, both SO3 and SOz remained solvated in the melt,
Alkali-metal Sulphates. Two separate s t ~ d i e s on
~ ~the
~ ncrystal
~ ~ ~structure of
lithium sulphate have confirmed the structure to consist of regular SO4
tetrahedra and fairly regular LiO, tetrahedra sharing corners, with average
sulphur-oxygen distances of 1.473 and lithium-oxygen distances of 1.961 A.
The crystal structure of thenardite, Na2S04 0 ,has been analysed and
refined.269At 25C the orthorhombic (Fddd) unit cell has the dimensions
a = 5.8596, b = 12.3044, c = 9.8170A. The crystal structure may be
described in terms of distorted NaO, octahedra and nearly regular SO,
tetrahedra. All S-0 distances in these are 1.476 f 0.001 A. Phase transformations in Na2S04, NaBrO,, and the double salt 5Na2S04,NaBr03have
been studied270in the temperature range 20-8OO0C. The double salt decomposes at 39OoC into Na2SOo and NaBr. The crystal structures of
K,Rbl,,HSOp
( x = 0.55) and RbHSO, have been determined.271 The
K,Rb,,HSO,
structure type has a layer-structure and exhibits the same
overall arrangement of alkali metals and sulphate groups within each layer
as RbHSO, in the (010) projection. These layers build into a three-dimensional
structure intermediate between that of KHS04 and RbHSO,. The structure
of RbHS04 (46) is composed of discrete sulphate tetrahedra and Rb+ ions
267
268
270
271
A. G.Nord, Chem. Comm. Uniu. Stockholm,1973, No. 3.

N. W. Alcock, D. A. Evans, and H.D. B. Jenkins, Acta Crysf.,1973, B29, 360.
A. G. Nord, Acra Chem. Scand., 1973, 27, 814.
C. Tkhiletkhy and S. K. Filatov, Russ. J. Inorg. Chem.,1972, 17,799.
W. G. Mumme, Acra Cryst., 1973, B29, 1076.
611
which are co-ordinated by shells of oxygen atoms. Rb(1) is nine-co-ordinate
with bonds ranging from 2.96 to 3.27 A (average 3.06 A). Rb(2) is ten-coordinate with bonds ranging from 2.91 to 3.15 A (average 3.05 A). Pairs of
Rb(1) polyhedra joined by edges at O(5)-O(5') and pairs of Rb(2) polyhedra
joined by edges at O(2)-O(2') are further joined to each other by corners at
O(8) to form chains.
The high-resolution S Ks emission spectra of S20E- and HSO, ions have
been measured.272The observed spectra were interpreted in terms of semiempirical MO calculations based on the extended Huckel and CNDO
approximations. The influence of the two sulphur atoms in two different
oxidation states was discussed in the case of S,O;- and the spectra of H S O p
and SO, were compared. The decrepitation of potassium and ammonium
persulphates has been
The rate of crystallization of sodium
thiosulphate from aqueous solution at 30 "C has been measured2', and an
expression for the rate of crystal growth determined. The Raman spectra of
aqueous solutions of Na2S04and MgSO, do not
any evidence for
ion-pair formation. Evidence for MgSO, and NaS0;i- ion-pairs was obtained
by the addition of Na and Mg salts to a solution of HSOp.
Alkaline-earth-metal Sulphates. The dehydration of BeS04,4H20 at various
by t.g.a., d.t.a., and X-ray diffraction techpressures has been
niques. The existence of the compounds BeS04,3H,0, BeS04,2H20, and
BeS04,H,0 was demonstrated. The thermal dissociation of anhydrous
BeSO, has been
At 630-640 "C a polymorphic transformation of
BeS0,is observed, and thermal dissociation takes place without a fusion stage.
An equation for the dissociation pressure of BeS0, in the temperature range
650-850 O C was derived and an activation energy of 47 kcal mol-f obtained,
The e.m.f. of the cell Ag,AgCl ICaCl,(m,),CaSO,(m,)~ Ca-exchange membrane ICaCl21AgC1,Ag has been used to determine278the dissociation constant
of CaSO, from 25 to 50 OC. The rehydration of hexagonal CaSO, has been
studied279in the temperature range 298-393 K at different water-vapour
pressures. The rate of rehydration was found to be strongly controlled by the
external water pressure. Natural strontium sulphate crystals have been
found280 to contain stable paramagnetic species and to give complex e.s.r.
spectra. The spectra could be classified into three groups, the first arising
from SO3 radicals, the remainder from lattice defects. The rate of reaction
E. K. Kortela and M. Karras, Spectrochim. Acta, 1973, 29A, 1293.
A. I. Lapshin, A. I. Serebrennikov, and 0. 0. Glazunov, Russ. J. Phys. Chem., 1972,
46, 28.
274 H . Kocova and V. Vaclava, Coll. Czech. Chem. Comm., 1972, 37, 3669.
275 F. P. Daly, C. W. Brown, and D. R. Kester, J. Phys. Chem., 1972, 76, 3664.
276 V. G . Vasilev, Z . V. Ershova, 0. N. Utkina, and N. T. Chebotarev, Russ. J . Inorg.
Chem., 1972, 17, 327.
w7 V. G . Vasilev and Z . V. Ershova, Rum. J. Inorg. Chem., 1972, 17, 330.
2 7 8 R. G . Ainsworth, J.C.S. Faraday I, 1973, 69, 1028.
279 M. C. Ball and L. S. Norwood, J.C.S. Faraday I, 1973,69, 169.
280 T. Matsuzaki, M. Setaka, U. V. Gromov, and T. Kwan, BUN. Chem. SOC.
Japan, 1972,
45, 2773.
272
273
40
612
between BaSO, and hydrogen has been measured281at 678 and 719 OC under
differing conditions. The rate of reduction was found to be significantly
affected by the presence of BaC03 in the sulphate, there being an almost
linear relationship with the content of the carbonate.
Other Metal Sulphates. The thermal behaviour of the double sulphate
Zn,A1,(S04),,36H20 has been studied.282Dehydration of the compound is
accompanied by its decomposition into zinc and aluminium sulphates, the
aluminium sulphate being hydrolysed to Al(OH)S04. The intensity of the
molecular scattering component of gaseous TI,SO, has been determined283
by electron diffraction at 700 OC. T12S04possesses a bicyclic structure with
D,, symmetry, the sulphate group being a regular tetrahedron with the angles
OSO 107.5" and OTlO 59". Sulphate fluorides of tervalent antimony with
alkali metals and ammonia have been prepared284with the composition
M2S0,,2SbF3 (M = K, Rb, or NH,), 3M,S04,4SbF3 (M = Rb, Cs, or NH,),
and M,S04,SbF3 (M = Na, K, or NH,).
Spectra and Phase Diagrams of Sulphate Systems. Spectroscopic studies on the
following compounds or systems have been published :the Na2S04,(NH,),S04,
MgS0,-H,O system;285the double sulphates Na2M11(S04),,2H,0286and
Table 1 Phase diagrams of sulphatesystems that have been studied

System
Li2S04-K2S0,-Rb,SO,-H,O
Li, Cs 11 NO3, SO,
Li, NH, 11 CO,, SO4-H20
2NaY2K,2T111 SO,
KzS208-KOH-H20
K2S0,-thiourea-H20
Reference
289
290
29 1
292
293
294
Na2S04-(NH4)2S04-Rb2S04-H20 295
296
Rb2S04-(NH4)2S04
297
Na2S0,-(NH,),SO,-CdS04-H20
298
(NH4)2sO,-Rb,SO,-H,O
299
K2S04-E u2(SO,) 3-H20
300
CS~SO~-(NH&SO~-H~O
Rb,S04-Al2(S04)3-H20
301
302
Rb, Cs )I C1, SO4
303
BaSO,, CaS04
A12(S04)3-CdS04-H20
304
305
A12(S0,),-ZnS0,-H,0
SrS0,-CaSO,
306
CaS0,-HN03-H2S04-H20
307
308
BeC1,-BeS0,-H20
MgSO4-HZS04
309
281
282
283
284
K. Mocek and E. Erdos, Coll. Czech. Chem. Comm., 1972,37,3386.

A. J. Moshinski, Rum. J. Inorg. Chem., 1972,17, 1527.
V. V. Ugarov, Yu, S. Ezhov, and N. G. Rambidi, Zhur. strukt. Khim., 1973,14,548.
R.L. Davidovich, L. A. Zemnukhova, and N. I. Sigula, Russ. J. Inorg. Chem., 1973,
18, 73.
V. N.Pilipchenko, L. P. Zharnovskaya, and V. M. Shpikula, Russ. J. Inorg. Chem.,
1972,17,1034.
S . Peytavin, G.Brun, L. Cot, and M. Maurin, Spectrochim. Acra, 1972,28A,1995.
613
Na2M11(S04),,4H20;287Li2S04,H,0 and Li2S04,D20.288
Phase systems for a
large number of sulphates have been studied and these are collected in
Table 1.289-309
Fluurusulphates. The synthesis and pyrolysis of some fluorosulphates has

been described.31 Peroxydisulphuryl difluoride has been found to substitute a
fluorosulphato-group for isolated hydrogen atoms in a fluorinated chain.
The reaction is initiated by the FS020 radical and proceeds under mild
conditions. The solubilities of some Group I and Group I1 fluorosulphates in
fluorosulphuric acid have been determined.311 The solubilities were rationalized on the basis of lattice- and solvation-energy considerations, the trends
being consistent with those observed for the corresponding fluorides in HF.
Interaction of XeF2 with the appropriate quantity of anhydrous acid has
been shown312to give FXeOS02F (colourless, m.p. 36.6 "C), Xe(OSO,F),
(pale yellow, m.p. 4 3 - 4 5 "C),FXeOS02CF3,and FXeOSO,CH, (colourless
solids). All the compounds are thermodynamically unstable, and the composition of the fluorosulphates provides for the synthesis of high-purity
S20,F2. The reaction of XeF, with fluorosulphuric acid does not give313a
xenon(1v) fluorosulphate but gives the xenon(1r) fluorosulphates FXeOS0,F
and Xe(OSO,F),. XeF,, however, gives the compound XeF50S02F on reaction with fluorosulphuric acid. The synthesis of some new methyltin(1v)
287
2s1
S. Peytavin, G. Brun, J. Guillermet, L. Cot, and M. Maurin, Spectrochim. Acta, 1972,

28A, 2005,
G . H. Price and W. I. Stuart, J.C.S. Faraduy I, 1973, 69, 1498.
I. N. Lepeshkov and I. M. Karataeva, Russ. J. Inorg. Chem., 1972, 17, 1755.
G . G. Diogenov and R. P. Mavridis, Russ. J. Inorg. Chem., 1972, 17, 449.
A. I. Partala, T. A. Slivko, V. E. Plyushchev, and V. P. Artemev, Russ. J. Inorg. Chem.,
1972,17,1043.
E. K. Akopov and V. G. Goryacheva, Russ. J. Inorg. Chem., 1972, 17, 1484.
293 J. Balej, Coll. Czech. Chem. Comm., 1972, 37, 3855.
2 9 4 A. K. Molodkin and 0.V. Geroleva, Rum. J. Inorg. Chem., 1972, 17, 1775.
2 9 5 0. A. Romanov and V. G . Shevchuk, Russ. J. Inorg. Chem., 1972, 17, 427.
as6 0. A. Romanov and V. G. Shevchuk, Russ. J. Inorg. Chem., 1973, 18, 335.
a97 A. S. Karnaukhov, T. P. Fedorenko, and V. G. Shevchuk, Russ. J. Inorg. Chem., 1972,
17, 294.
0. A. Romanov and V. G. Shevchuk, Russ. J. Inorg. Chem., 1972,17,1486.
299 A. I. Barabash, L. L. Zaitseva, andV. S. Ilyashenko, Russ. J. Inorg. Chem., 1972, 17,
1039.
300 Yu. V. Ushakov, Russ. J. Inorg. Chem., 1973, 18, 146.
301 V. G. Shevchuk and A. A. Maksimenko, Russ. J. Inorg. Chem., 1972,17,133.
=02 E. K. Akopov and T. P. Borntnikova, Russ. J. Inorg. Chem., 1972,17, 926.
303 0. Vojtech, J. Moravec, and I. Krivy, J. Inorg. Nuclear Chem., 1972, 34, 3345.
304 A. S. Karnaukhov,T. P. Fedorenko, and V. G. Shevchuk, Russ. J. Inorg. Chem., 1973,
18, 152.
305 A. S. Moshinskii, Russ. J. Inorg. Chem,, 1972, 17, 598.
ao6 0. Vojtech, J. Moravec, and I. Krivy, Inorg. Nuclear Chem. Letters, 1973, 9, 863.
307 B. A. Beremzhanov and V. P. Kruchenko, Rum. J. Inorg. Chem., 1972,17, 1036.
308 M. I. Vaisfeld and V. G. Shevchuk, Russ. J. Inorg. Chem., 1972, 17, 1638.
30s A. B. Zdanovskii and G. A. Murav'eva, Russ. J. Inorg. Chem., 1972, 17, 1746.
310 C. G. Krespan, J. Fluorine Chem., 1972, 2, 173.
311 R. Seeley and A. W. Jacke, J. Fluorine Chem., 1973, 2, 225.
312 M. Wechsberg, P. A. Bulliner, F. 0. Sladky, R. Mews, and N. Bartlett, Inorg. Chem.,
1972,11, 3063.
313 D. D. Desmarteau and M. Eisenberg, Inorg. Chem., 1972, 11, 2641.
614
chlorosulphonates and trifluoromethanesulphonates of the general type

Me,SnCl,(SO,X),~,,,
(where n and m may be 0, 1 , or 2 and X = F or
CF,) have been describedP4 Vibrational spectra showed that all the compounds contained only bidentate S03F groups, possibly acting as bridging
groups and giving rise to polymeric chain or sheet-like structures.
Su1phites.-The i.r. spectra of several metal sulphites of known crystal
structures have been examined315and the predominant co-ordination of the
sulphite ion has been correlated with the spectra. A stretching mode of high
intensity above 975 cm-l indicates co-ordination through sulphur and conversely a mode with high intensity below 960 cm-l signifies co-ordination
through oxygen. Stretching frequencies around 975-960 cm-l indicate that
the compound is either ionic or has the sulphite group engaged in covalent
bonding with bonds to both oxygen and sulphur, e.g. NH4CuS03. The
sulphur Ks X-ray emission spectra of SO$- and SO,F- ions have been
studied316in detail and the observed fine structure has been interpreted with
the aid of MO calculations. The different MO methods were compared
with regard to their success, and the effect of d-orbitals on the bonding was
discussed. E.s.r. experiments317have confirmed that the direct photolysis of
aqueous solutions of sulphite yields SO3 ions and a hydrated electron.
Liquid SOz reacts318 with aqueous NR40H (R = Et, Bun, or n-pentyl)
solutions to form the corresponding bisulphite. The bisulphite ion HSO: in
these compounds has essentially C,,symmetry. It was thought that the large
cations stabilize the bisulphite ion relative to the SzOg- ion since the lattice
energy of the tetra-alkylammonium bisulphite is probably sufficient to overcome the tendency of the dimeric ion (47) to lose water and form the pyrosulphite ion.
'H
'
yo
0
'
The compound CaSO3,$HZOcrystallizes319in the space group Pbna, with

the cell constants a = 6.4844, b = 9.8123, and c = 10.6629 A. The hydrate
MgSO3,2HZO,has been preparedsz0by mixing aqueous solutions of MgCl,
P. A. Yeates, 5. R. Sans, and F. Aubke, Inorg. Chem., 1972, 11, 2634.
B. Nyberg and R. Larsson, Actu Chem. Scund., 1973, 27, 63.
316 S. Aksela and M. Karras, Chem. Phys. Letters., 1973, 20, 356.
317 0. P. Chawla, N. L. Arthur, and R. W. Fessenden, J. Phys. Chem., 1973, 77, 772.
318 R. Maylor, J. B. Gill, and D. C. Goodall, J.C.S. Dalton, 1972, 2001.
31s L. Schropfer, 2. anorg. Chem., 1973,401, 1.
3a0 T. B. Kovachev, V. D. Bakalov, and D. Trendafelov, Dokludy Bolg. Akud. Nu&,
1973, 26, 63.
314
315
615
and Na2S03. 1.r. data indicate that the dihydrate has the structure
Mg(HSO,)OH,H,O. The compound MgS0,,6H20 has been shown321 to
crystallize in the hexagonal space group R3, with a = 8.830 and c = 9.075 A.
The structure consists of a slightly distorted CsCl arrangement of octahedral
[Mg(H20),l2+ and pyramidal SO:- ions. The crystal structure of silver
sodium sulphite dihydrate, AgNaS03,2H20, has been
The
silver atom is nearly linearly co-ordinated by the sulphur atom and one of the
oxygen atoms of the sulphite group. This results in a chain-like structure for
the AgS03 group, with the bond distances Ag-S = 2.474 and Ag-0 =
2.194 A. The sodium atom is octahedrally co-ordinated by 3 sulphite-oxygen
atoms and 3 oxygen atoms of the water molecules, with an average Na-0
bond distance of 2.148 A. The average dimensions of the SO;- ion are S-0
1.522 8, and the OSO angle is 106.3'. The degradation of Na,S204 in air has
been
to be greatly influenced by the humidity, presumably because
the reaction involves an oxidative decomposition with oxygen and water to
NaHSO, and NaHSO,.
A kinetic equation for the disproportionation of solid BaSO,:
4BaS03 --+ Bas
+ 3BaS0,
has been proposed324which expresses the reaction rate as a function of the

solid phase composition, temperature, and partial pressure of water vapour.
The rate constant is, however, a linear function of the partial pressure of
water vapour, which is thought to act as an oxygen carrier. The rate of
reduction of solid BaSO, by hydrogen has been measured325under different
conditions at temperatures between 640 and 700 "C.The experimental data
may be interpreted by a mechanism involving firstly the disproportionation of
BaS0, and then the reduction of the sulphate to Bas by hydrogen. A kinetic
analysis of the above reaction has also been carried
The reaction between cyanogen chloride and sulphite ions has been shown327
to involve the formation of a stable adduct. Reactions were carried out
between sulphur dioxide and an excess of cyanogen chloride in aqueous
solution; on raising the pH to 8 or 9 the sulphite ions react slowly with the
cyanogen chloride to produce the adduct, which slowly decomposes to give
cyanate, C1-, and SO;- ions. Kinetic evidence suggests that the adduct
contains cyanogen chloride and sulphite ions in the ratio of 2:2, and to
account for the stability at pH < 9 a cyclic structure (48) is likely, with a
six-memberedS-N-C
ring. Scheme 1 was suggested to describe the reaction.
321
322
323
324
335
326
H. Flack, Actu Cryst., 1973, B29, 656.
L.Niinisto and L. 0. Larsson, Actu Cryst., 1973, B29, 623.

F. Endo, K. Sakaino, M. Hirokado, M. Tamura, Y . Handa, and T. Fujii, Tokyo
Toritsu,Eisei Kenkyusho Kenkyu, Nenpo., 1973, 23, 241.
K. Mocek and E. Erdos, Coll. Czech. Chem. Comm.,1972,37, 3376.
K. Mocek and E. Erdos, Coll. Czech. Chem. Comm.,1973,38,7.
K. Mocek and E. Erdos, Coil. Czech. Chem. Comm., 1973, 38, 16.
616
2-
20H-
...
&
CI-C=N--S-O
Reagents: i, SO:- ;ii, 2H'; iii, CNCl
Scheme 1
The disproportionation of aqueous dithionate is known to take place at

high temperatures in a slow, acid-catalysed reaction :
H+
+ -O,S-SO,
SO
+ HSO;
A recent studf2* has shown that the same reaction may take place smoothly
at room temperature in 7-1OM-H2SOp. Redox potentials of aqueous
solutions containing dithionite, sulphite, and t h i o ~ u l p h a t eand
~ ~ ~for the
irreversible system sulphite-dithi~nite~~~
have been measured.
The crystal structure of potassium barium hexathionate K,Ba(S,O,), has
been
The space group is P2/c, with cell constants a = 11.591,
b = 10.835,c = 9.145A, and /I= 111.93O.The six-membered sulphur chain
of the hexathionate anion has the cis-cis rotational isomeric form (49)
(49)
Sulphuric Acid and Related Systems.-The chemistry of superacid systems

has been r e v i e ~ e d . 3The
~ ~ review includes discussion of sulphuric acid,
fluorosulphuric acid systems, and cations of sulphur, selenium, and tellurium
328
3aB
330
331
338
W. Y. W. Lew and R. E. Powell, Inorg. Chem., 1973,12,957.

A. Teder, Acta Chem. Scand., 1973, 27, 705.
A. Cugnac-Pailliotet, M . 4 . Gadet, and J. Pouradier, Compt. rend., 1973,276, C, 1331.
K. Maray, Acta Chem. Scand., 1973, 27, 1684.
R. J. Gillespie, Endeuoour, 1973, 32, 3.
617
in sulphuric acid oleum. Hammett acidity functions have been determined333
for a variety of superacid systems. The radical SO;, produced by the direct
effect of radiation on H,SO4, has been observed334in aqueous 0.4M-,
2M-,
and 4M-H,S04.
The reaction of potassium aluminate with H,SOp at 25C has been
The crystal structure of trifluoromethanesulphonic acid,
H30+CF3S0~,
at 298 and 83 K has been determined.336The structure comprises oxonium ions and trifluoromethanesulphonate ions hydrogen-bonded
together to form layers. The extraction of H2S04by methyl diphenyl phosphate
and tributyl phosphate has been investigated.337The experimental data are
consistent with the formation of the complex [H(H,O),(MePh,PO,)$] [HSO,]
at acid concentrations up to 10 moll-l. At higher concentrations, complete
miscibility of MePh,PO, and H2S04 is observed. The behaviour of some
lead@) and tin(Iv) compounds in disulphuric acid has been
Other Sulphur-containing Compounds.-The e.s.r. spectrum of NaSO, trapped
~ ~ compound is prepared by the
in argon at 4 K has been m e a ~ u r e d . 3The
codeposition of sodium atoms and SO2. From the observed data, NaS02 is
non-planar, with the Na+ ion located 4.3a0 from each of the oxygen atoms
and 4.700 from the sulphur atom.
The i.r. absorption spectra of aqueous, acetone, and methanol solutions of
the complexes CSZ~(NCS)~,H,O,
KCs [Cd(SCN),],H,O, Cs, [Cd(SCN),],H,O,
K,Cd(SeCN),X, (X = C1, Br, or SCN), and K,Cd(SeCN),I,Me,CO have
been studied.340In aqueous solutions of the zinc complex the NCS- group is
co-ordinated through the nitrogen atom; in the cadmium complexes isomerization is observed, with sulphur co-ordination in aqueous solution,
nitrogen co-ordination in methanol solution, and both forms of co-ordination
observed in acetone solution. Rates and products of the reaction of S(CN),
with the ion SCN- have been determined.341The results are consistent with
the formation of the species (SCN), as an intermediate. Irradiated KCNS
gives an e.s.r. spectrum which may be interpreteda2 in terms of the dimeric
ion (NCS)z and the anion NCS2-. The radical (NCS)? is assigned a linear
structure (50) rather than the bent configuration (51).
Lattice vibrational spectra of five polymorphic forms of thiourea have been
R. J. Gillespie and T. E. Peel, J. Amer. Chem. SOC.,1973, 95, 5173.
B. Lesigne, C. Ferradini, and J. Pucheault, J. Phys. Chem., 1973, 77, 2156.
335 S. V. Gerorkyan, D. G. Aslanyan, S. T. Kostanyan, and L. H. Khachatryan, Russ. J .
Inorg. Chem., 1972, 17, 808.
336 J. B. Spencer and J. 0. Lundgren, Acta Cryst., 1973, B29, 1923.
337 A. Apelblat, J.C.S. Dalton, 1973, 1198.
338 R. C. Paul, J. K. Puri, and K. C. Malhotra, J. Inorg. Nuclear Chem., 1973, 35, 403.
33n F. J. Adrian, E. L. Cochran, and V. A. Bowers, J . Chem. Phys., 1973, 59, 56.
340 A. Yu. Tsivadze, Ya. Ya. Kharitonov, and G. V. Tsintsadze, R u n . J. Inorg. Chem.,
1972,17,1529.
8 4 1 D. F. Kerr and I. R. Wilson, J.C.S. Dalton, 1973, 459.
3 4 2 I. S. Ginns and M. C. R. Symons, J.C.S. Dalton, 1973, 3.
333
334
618
N-C-EL-S-C-N-
N-C,
measured.343A studyM4of the thermal decomposition of some metal mercaptides M(SC,X,) (X = F or C1, M = alkali metal) has shown that the reaction proceeds according to the equation:
The crystalline thiocarbonates BaCS,, Tl,CS3, PbCS, (two modifications),

and CdCS, have been preparedx5 and their i.r. spectra recorded.
In acid solution Spot- has been shownM6to react with S,P,046- to form
the higher polysulphane diphosphonates S3P20$- and S,P,O$-. The reaction347
of polysulphane disulphonates with SPOg- in acid solution yields polysulphane diphosphonates and polysulphane phosphonosulphonates. The formation of these compounds depends on the nucleophilic attack of the SPOgon the sulphur chains of the starting materials, during which, growth of the
sulphur chains occurs.
Details for the synthesis of bis(trifluoromethy1) sulphoxide CF,S(O)CF,
have been given.348The reaction of HNF,,KF with sulphinyl fluoride has
been shown349to give the compound FS(O)NF,, which may be isolated
and has sufficient stability to be characterized by spectroscopic methods.
Attempts to prepare CF,S(O)NF, and C,F,S(O)NF, resulted in the formation
of NzFa, CF,S02SCF3, and C2F,S0,C2F5. The liquid-phase Raman spectra
of CF,SCF,, CF,S(O)CF,, and CF,SSCF, have been rep0rted.3~~
Assignments were made on the basis of the previously reported symmetries of C,,
and C2 for CF,SCF, and CF,SSCF3, respectively, and an assumed C,
symmetry for CF3S(0)CF3. In reactions with perfluoroalkylsulphenyl
chlorides (RSCl) and perfluoroalkyl disulphides (RSSR), chlorine monofluoride has been shown35fto act as a chlorinating and fluorinating agent to
give the corresponding perfluoroalkylsulphur chloride tetrafluorides, RSF4Cl,
in good yields, with small amounts of perfluoroalkylsulphur pentafluorides
(RSF,). The fluorination of perfluorotetramethylenesulphide with ClF under
controlled conditions results352in the formation of both sulphur(1v) and
sulphur(v1) compounds. PerfIuorotetramethylene sulphur tetrafluoride was
343
344
345
346
347
348
349
360
351
362
A. Bandy, G. L. Cessac, and E. R. Lippincott, Spectrochim. Acta, 1972, 28A, 1807

M.E. Peach, J. Inorg. Nuclear Chem., 1973, 35, 1046.
J. Horn and W. Sterzel, 2.anorg. Chem., 1973, 399, 21 1.
E.Blasius and N. Spannhake, 2. anorg. Chem., 1973, 399, 315.
E. Blasius and N. Spannhake, 2.anorg. Chem., 1973,399, 321.
D.T.Sauer and J. M. Shreeve, Inorg. Synth., 1973, 14,42.
R. A. De Marco and J. M. Shreeve, Inorg. Chem., 1973,12, 1896.
H.A. Carter, C. S.-C. Wang, and J. M. Shreeve, Spectrochim. Acta, 1973,29A,1479.
T.Abe and J. M. Shreeve, J . Fluorine Chem., 1973, 3 , 187.
T.Abe and J. M. Shreeve, J . Fluorine Chem., 1973,3 , 17.
619
found to be very stable to thermolysis and chemical attack, but the hydrolysis
of the novel perfluoromethylenesulphur difluoride gives perfluorotetramethylene sulphoxide, and its pyrolysis gives perfluoro-(di-n-butyl)
disulphide.
3 Selenium
The Element.-A review (with no references) has been

on the
phase transformations, energy band structure, photoconductivity, e.s.r., and
electrical properties of selenium. Two methods for the determination of
selenium by atomic absorption methods, following conversion into a volatile
hydride by NaBH4,354and also incorporating a reducing agent (TiCI3 and
Mg),355have been devised. Highly pure (99.998 %) and commercial selenium
have been studied by d.t.a.356A number of thermal effects were observed and
interpreted. Increasing the purity of selenium was found to narrow the
temperature region of the amorphous state. The number of thermal effects
observed between 40 and 120C was found to depend on the quenching
temperature, decreasing with an increase in the latter. The crystallization
region extends between 100 and 2OO0C, the liquid state from the melting
point to 650 OC. A number of effects due to dissociative-associative processes
were observed on cooling from 650 "C.The vapour pressure of liquid selenium
(also S and Te) has been determined357by a static method in the pressure
range 4-760 mmHg. Selenium undergoes a semiconductor to metal transition under pressures of about 130 kbar, with superconductivity also being
has shown that the metallic state
observed at this pressure. A recent
is not retained, and hence selenium is not a superconductor after the release
of high pressure at room temperature. Resistance measurements imply that
the semiconductor to metal transition is, however, readily reversible at
130 kbar. The texture of rolled selenium has been c h a r a ~ t e r i z e d .The
~~~
recrystallization texture of plastically deformed selenium was found to be
the same as that after deformation and it was shown that texture has an important effect on the resistivity of selenium.
A comparison has been made360of the radial atomic distribution functions
of three forms of selenium; the liquid at 250 and 350C, the amorphous
solid (quenched from 550 to OC) at 2OoC, and as hexagonal crystals at
ambient temperature. In the liquid, the number of parallel atomic chain
353
364
355
356
357
368
36s
360
G . V. Abdullaev Vestnik. Akad. Nauk S.S.S.R., 1972, 25.

F. J. Schmidt and J. L. Royer, Aizalyt. Letters, 1973, 6, 17.
E. N. Pollock and S. J. West, Atomic Absorption Newsletter, 1973, 12, 6.
N. M. Talvidis, B. G . Strongin, and N. S. Parasinchuk, Izvest. Akad. Nauk. S.S.S.R.,
Neorg. Materialy, 1973, 9, 176.
Yu. S. Chernozubov, B. P- Kuznetsov, A. A. Klimenko, and E. V. Podmogilnyi,
Russ. J . Phys. Chem., 1972, 46, 168.
J. Wittig, J . Chem. Phys., 1973, 58, 2220.
K. P. Mamedov, S. B. Bagirov, and G . Sh. Gasanov, Soviet Phys. Cryst., 1973,17,902.
J. Mosanski, A. Renninger, and B. L. Averbach, Phys. Letters (A), 1973,42,453.
620
configurations (characteristic of hexagonal selenium) decreased with increasing temperature as configurations with smaller numbers of atoms were
formed. No parallel-chain configurations were observed in the amorphous
solid. The observed configurational changes could involve the formation of
small molecular rings or a reduction in the average chain length. The effects
of hydrostatic pressure on the first-order Raman frequencies of selenium and
tellurium have been reported;361 all the frequencies of the Raman-active
modes were found to decrease with increasing pressure. The electronic energy
structures of chains and rings of selenium have been calculated362by a MO
approach, i.e. using the hybrid orbitals as bases and using the semi-empirical
Hamiltonian matrix elements. The calculated density of states is in excellent
agreement with that obtained for amorphous selenium by photoemission
experiments. The effect of pressure on the reaction PF3 X -+ XPF,
(X = Se, 0, S , or Te) has been
With selenium a 50% conversion
into SePF, was obtained at 4000 atm and 300 "C,this light-sensitive material
decomposing to red amorphous Se and PF, at room temperature. No reaction was observed between PF, and Te at 300 OC and 4000 atm.
A series of heteronuclear, magnetic double-resonance experiments364have
been performed on a wide range of molecules containing selenium. The signs
of the coupling constants involving selenium are usually unaffected by changes
in the valency of selenium. The study does indicate, however, that if all the
lone-pairs of the selenium are used for bonding, there may be a sign inversion.
The Oxides of Selenium.-The gas-phase absorption spectrum of SeO, has

been investigated365for the three isotopic species 75Se160,, 80Se1602,and
78Se1s0,. Spectra were recorded between 130 and 200 O C , the decomposition
of the oxide being suppressed by the addition of oxygen to the system, and
many additional bands were thereby revealed. The reaction of gaseous SeO,
with zinc sulphide has been
at 300-700 O C and an SeO, concentration in the gas phase of 200mg1-l. The observed solid products were
ZnSe, ZnSO,, ZnSe03, ZnO, and elemental selenium. The primary products
of the reaction were thought to be ZnSe and ZnSO,:
+ SeO, -+ ZnSe + SO2

+ 2Se0, -+ ZnSO, + 2Se
ZnS
ZnS
A further series of reactions, under conditions similar to those above, carried

out between ZnSe and SeO,, ZnS and ZnSeO,, ZnS and ZnSO,, and ZnSe
361
362
363
364
365
366
W. Richter, J. B. Renucci, and M. Cardona, Phys. Status SoIidi (B), 1973, 56, 223.
I. Chen, Phys. Rev. (B), 1973,7, 3672.
A. P. Hagen and E. A. Elphingstone, Inorg. Chem., 1973, 12, 478.
W. McFarlane and D. S. Rycroft, J.C.S. Chem Comm., 1973, 10.
G. W. King and P. R. McLean, J. Mol. Spectroscopy, 1972, 44, 403.
V. M. Goryaer, V. V. Pechkovskii, and G. F. Pinaer, Russ. J . Inorg. Chem., 1972, 17,
18.
621
and ZnSO, suggested that the following reactions also take place:
+ +SeO, -+ ZnO + 1$Se

ZnSeO,
ZnO + SeO,
3ZnS + 4ZnSe0, + 3ZnSe + 2ZnS0, + 2Zn0 + Se + so,
ZnS + 3ZnS0,
4Zn0 + 430,
ZnSe + ZnSO, -+ 2ZnO + Se + SO,
ZnSe
-+
--+
Reactions between ZnO and low concentrations E0.03 (mg Se) -l] of gaseous
SeO, in a carrier gas have also been st~died.3~'
A thermogravihetric and gas-volumetric study368 has shown that the
thermal decomposition of SeO, takes place in two stages with the formation
of an intermediate pentoxide and the evolution of the stoicheiometricquantity
of oxygen. It was also observed that SeO, begins to decompose at a lower
temperature in a nitrogen atmosphere than in oxygen. Selenium trioxide has
been shown369to form 1:l complexes with organic bases such as pyridine,
y-picoline, quinoline, morpholine, and triethylamine, in liquid SOz or
nitromethane. The complexes were found to be of the donor-acceptor type
and i.r. studies suggest that selenium is co-ordinated via the nitrogen atom of
the tertiary base, and that the tetrameric ring of SeO, is retained in the
adducts.
Selenium-Halogen Compounds.-Perfluoroethyl selenium trifluoride is produced,3'O in almost 100% yield, by the reaction of bis(perfluoroethy1) diselenide with chlorine monofluoride in a 1 : 6 ratio. Like SeF,, C2F,SeF,
forms 1:l adducts with CsF and SbF, which are best formulated as
Cs+C2F,SeF; and C,F,SeF$SbK, respectively. C2F,SeF, is oxidized by CIF,
at ambient temperatures, according to the equation:
C2F,SeF3
+ ClF
4truns-CzF,SeCIF,
Several perfluoroalkyl derivatives of SF, and SF6 are known, but this appears
to be the first report of the preparation of perfluoroalkyl derivatives of SeF,
and SeF,.
The vibrational spectra of (a) selenium tetrafluoride in the vapour and solid
phases, and isolated in inert-gas matrices, and (b) tellurium tetrafluoride, in
both the solid and matrix-isolated condition, have been rep0rted.37~The
fundamental frequencies were assigned on the basis of the C,, symmetry of
discrete SeF, and TeF, molecules ;force constants, obtained by normal-coordinate analysis, showed that the axial bonds are weaker than the equatorial
367
388
36e
370
s71
G. F. Pinaer, M. I. Berezina, V. V. Pechkovskii, and R. Ya. Mel'nikova, Russ. J.

Inorg. Chem., 1972, 17,26.
E. E. Sidorova, S. N. Kondratev, K. N. Mochalov, G. I. Blagoveshchenskaya, and
K. P. Pribylov, Russ. J . Znorg. Chem., 1972, 17, 157.
R. C. Paul, R. D. Sharma, and K. C. Malhotra, Indian J. Chem., 1972,10,428.
C. D. Desjardins, C. Lau, and J. Passmore, Innorg. Nuclear Chem. Letters, 1973, 9 ,
1037.
C. J. Adams and A. J. Downs, Spectrochim. Acta, 1972, 28A, 1841.
622

bonds. Studies on more concentrated matrices or on diffusion of the monomeric species indicated the presence of bridging interactions involving only
the axial M-F bonds, leaving the equatorial MF2 units largely unchanged.
Possible structures of the SeF, and TeF, dimers are shown in (52) and (53).
(52)
(53)
Conductimetric measurements have

that SeF, is a weak base in
liquid HF, with an ionization constant of 4 x lo-,. The adduct SeF,,BF,
ionizes in H F but the solutions have a lower conductivity than those of
SFiBF,. It is concluded that SeF4,BF3is both polymeric and incompletely
ionized in solution in HF. The 19F n.m.r. spectra of the pentafluoro-orthoselenium and pentafluoro-orthotellurium groups have been shown3', to have
the characteristic AB, pattern. The different possible bondings are discussed
on the basis of the observed chemical shifts, and a trans-effect, with the axial
fluorines being most influenced, is observed.
SF, is well known to be an abundant source of negative ions as a result of
electron bombardment. A comparison has been made374of the negative ions
formed by SeF,, TeF,, and WF,. The parent ions SeF, and TeF, were not
observed in mass spectra at low electron-energies (0-10 eV), in marked
contrast to SF,, but were observed in the presence of SF, at pressures of
Torr. A comparison of the dissociation energies for the various ions
indicated that the captured electron is in a bonding orbital for SeF,, TeF,,
SeF;, and TeFz, and in a non-bonding orbital for SeFF and TeF,.
The reaction of Se(OMe), with Sex4 (X = Cl or Br) in the molar ratio
3 :1 has been
to give compounds of the type (MeO),SeX (X = C1 or
Br). The chlorine atom in (MeO),SeCl may be replaced by F or NO, by
metathetic reaction with AgF or AgNO,; reaction with AlCI, yields the compound (MeO),SeAlCl,. Some properties of the above compounds and their
i.r. spectra are given and some deductions concerning the nature of the bonding are made from the i.r. data. With a view to understanding the properties
of selenium monochloride, a number of the adducts of Se2C12with Lewis
acids and bases have been prepared376and their properties studied. Adducts
372
373
374
376
3 7
M. Brownstein and R. J. Gillespie, J.C.S. Dalton, 1973, 67.

K. Seppelt, 2. anorg. Chem., 1973,399, 65.
P. W. Harland and J. C. J. Thynne, Inorg. NucIear Chem. Letters, 1973, 9, 265.
M. Reichenbacher and R. Paetzold, 2. anorg. Chem., 1973, 400, 176.
~
R. C. Paul, R. D. Sharma, R. K. Verma, and K. C. Malhotra, Indian J. Chem., 1972,
10,737.
623
such as Se,CI,,BCI, and Se2CI,,SbC15 have been isolated at -40C when
components are mixed in liquid SO,. The i.r. data show that Se2Cl, acts as a
strong chloride-ion donor in the presence of strong chloride acceptors.
Adducts of Lewis bases are ionic in nature, with the nitrogen atom of the
tertiary bases acting as the donor and Se as an acceptor.
The selenium-iodine phase diagram has been constructed377using d.t .a.
methods. No chemical reaction was observed between Se and I, in the
1-90 atom% I range in the solid and liquid states. A continuous series of
solid solutions are formed in the SbSeI-SbSI system.378Experimental data
(X-ray, phase, and thermal analysis) suggest that substitutional solid solutions
are formed, the replacement of sulphur atoms by selenium atoms resulting in
a h e a r change in the lattice parameters. The compounds Pb4SeBr6,Pb5S216,
and Pb,S,Br,, have been shown379to possess common structural features with
the pure halides of lead. In Pb,SeBr, all the lead atoms have trigonal prismatic co-ordination by Br and Se, with additional neighbours above the prism
faces bringing the co-ordination number to 7, 8, or 9. In Pb5S21,some of the
lead atoms have the same extended prismatic arrangement, others are at the
centres of PbI, octahedra. Pb7S2Brlois isostructural with Th7Sl,.
The gas-phase i.r. spectra of the molecules SeOF,, SeOCl,, and SOCI, have
been measured and assigned.380Force constants and potential-energy distributions have been calculated on the basis of the general valence force field.
The preparation of several compounds containing the pentafluoroselenium
group has been announced. From the reaction of pentafluoro-orthoselenic
acid and SO, only one compound containing the pentafluoroselenium group
could be prepared:381
2F,SeOH
+ 4S0,
--f
SeO,F,
+ 2FSOSH + F,SeO-SO,-OS0,F
The 19F n.m.r. spectra of F,SeO-SO,-OS0,F

showed a coupling taking
place over a range of six bonds. The reaction of mercury bis(pentafluor0orthoselenate) with trifluoroacetyl chloride was shown to yield pentafluoroorthoselenic acid trifluoroacetate :
Hg(OSeF,),
+ 2CF3COC1 -+ HgCla + 2F,SeO-CO-CF3
The reaction of SeO, with fluorine has been shown382to produce not only
SeF,OOSeF, but also a substantial proportion of SeF50SeF,. Bis(pentafluoroselenium) oxide is relatively stable and resistant to hydrolysis. The new
compound, pentafluoroselenium fluorosulphate (SeF,OSO,F), may be prepared by the reaction of SeF,OOSeF, and peroxydisulphuryldifluoride
377
378
378
380
381
382
S. N. Chizhevskaya, H. K. Abrikosov, and B. B. Azizova, Izvest. Akad. Nauk.

D. P. Belotskii, Ya. I. Gorchinskii, and N. P. Novalkovskii, Dopovidi Akad. Nauk.
Ukrain. R.S.R., Ser. B, 1972,34, 1079.
B. Krebs, 2. anorg. Chem., 1973, 396, 137.
G. Hopf and R. Paetzold, 2.phys. Chem. (Leipzig), 1972, 251, 273.
K. Seppelt, Chem. Ber., 1972, 105, 3131.
W. L. Reichert and G. 3. Cady, Inorg. Chem., 1973, 12, 769.
624
(S20,F,). The compound SeF,OOSeF, decomposes at a much lower temperature (85 "C) than the sulphur analogue (200 "C). Both compounds
probably decompose to the SeF,O' and SF,O' radicals, but the SF,O'
radical may give rise to many compounds containing the SF,O group whereas
SeF,O' breaks up, probably to SeF,' radical. The formation of SeF,OSeF,
may thus result from the combination of SeF,' and SeF,O' radicals and
SeF,OSO,F from SeF,' and SO,F' radicals. The preparation and properties
of the compounds F5SeOCl, F,SeOBr, (F,SeO),Br, and of the known compound F,SeOF have been d e ~ c r i b e d The
. ~ ~ peroxide F,SeOOSeF, is a byproduct in the synthesis of F,SeOF, and the formal anhydride of pentafluoroselenic acid, F,SeOSeF,, is the main product from the decomposition of the
xenon salt (F,SeO),Xe. Iodine compounds such as F&OI and (F,SeO),I are
not stable but may be identified by 19Fn.m.r. spectra. The vibrational (i.r.
and Raman) spectra of F,SeOH, F,SeOF, F,SeOCl, and F,SeOBr have
been measured and discussed.384The acid F,SeOH has nearly the spectrum
of an octahedron and the high selenium-oxygen vibration frequency of
the anion F,SeO- is explained. The new compounds Rb+[Br(OSeF,),]-,
NO2-OSeF,, and F,SeOSeOOSeF, have been prepared3*,
NOt [OSeF,]to demonstrate the reactivity of the OSeF, group. The new derivatives
BrOTeF, and I(OTeF,), are compared with the homologous selenium compounds, and the differences between the compounds were explained.
Se1enides.-E.m.f. measurements on cells of the type, LilLi halide eutectic

mixturelLi in Se, have been
to determine thermodynamic quantities
for the Li-Se system. For low concentrations of lithium in the cathode, the
overall reaction is :
2Li
+ xSe
--+
Li,Se,
From cell data, the activity coefficient of lithium is 6 x

in the dilute
lithium region and the standard free energy of formation of Li,Se at 360 "Cis
-94.0 kcal mol-l.
Group 111 Element Selenides. The electronic spectrum of the vapour over
B2Se3 Se or B Se mixtures at 12OO0C has been mea~ured.3~'
The
numerous diffuse bands observed were attributed to the BSe, molecule. The
i.r. absorption spectra of In,Se, Tl,Se, Ga,S, In,S, In,Te, and T1,S in the gas
in the
phase at temperatures between 850 and 1400C have been
range 200-2000 cm-l. The electronic band structure of the layer compound
GaSe has been calculated389using the empirical pseudopotential method. The
s83
s84
s85
388
387
s88
38s

K. Seppelt, 2. anorg. Chem., 1973, 399, 87.
E. J. Cairns, G. H. Kucera, and P. T. Cunningham, J . Electrochem. Soc., 1973, 120,
595.
V. A. Koryazhkin, Vestnik Moskov. Univ., Khim.,1972, 13, 719.
V. A. Shevelkov, Yu. S. Ryabov, and A. A. Maltsev, Vestnik Moskov. Univ., Khim.,
1972, 13, 645.
M . Schlueter, Nuouo Cimento, 1973,13, 313.
625
selenide Ga2Se, has been shown390to exist in three polymorphic modifications,

the change from one modification to another being accompanied by a slight
change in density. A region of solid solutions based on Ga,Se, was also
observed in the ternary Ga-Sb-Se system. The reaction of gallium with
selenium to form the compound Ga,Se has been studied391by recording the
heating curves. The formation of Ga,Se, from molten gallium and selenium
vapour, was observed at temperatures between 780 and 850 "C.Ga,Se melted
at 920 'C, underwent a peritectic decomposition at 930 "C, and GaSe melted
at 950 OC. X-Ray data showed Ga,Se to have a cubic structure with a unit cell
containing 10 molecules and a dimension of 8.918 A. Both components of the
TlSeGaSe system have been shown3g2to melt without a peritectic decomposition, and neither undergoes a phase transition.
The crystal structure of InpSe, has been determined393from three-dimensional
X-ray diffractometric data. The crystals are orthorhombic in the space group
Pnnm, with unit-cell dimensions a = 15.297, b = 12.308, c = 4.081 A. The
structure is composed of endless interlocking chains running parallel to the
c-axis. The chains, which consist of five-membered In-Se rings, are crosslinked by strongly bound In-In-In
units to form a continuous sheet perpendicular to the a-axis. The presence of very short bonds (2.77 A) in the
In-In-In
unit indicates that the structure contains the homonuclear (In,)*
cation, with the selenium atoms in the doubly ionized state. Thermodynamic
functions of In2Se(,)have been calculated394in the temperature range 273.152000 K. A single-crystal
has confirmed that the compounds TlGaTe,,
TlInSe,, and TlInTe, crystallize in the TlSe type of structure. As a univalent
cation, thallium is surrounded by 8 chalcogen atoms; gallium and indium are
tervalent with tetrahedral co-ordination and covalent bonding. Crystal data
have been presented for the ternary selenides TlGaSe, (P2,,m; a = 7.60,
b = 7.60, c = 31.36 A; i3 = 9020')396 and CuInSe, (142d; a = 5.782,
c = 11.620
The system Ga,Se,-L,Se,
(L = lanthanide element or
yttrium) has been ~ t u d i e d . 3Two
~ ~ types of compound were observed; for
L = Gd to Dy, phases of the type LGaSe, were found, whilst for L = La to
Gd, the general formula was L,Galo,,Sel,.
Grpup ZV Element Selenides. An improved method for the synthesis of CSe,,

by a refinement of the Ives reaction:
CHzClz
3D0
391
392
393
394
+ 2Se
---f
CSez
+ 2HC1
P. I. Fedorov, E. I. Smarina, and A. V. Roshchina, Uch. Zap. Mosk. Inst. Tonkoi.

Khim. Technol., 1971, 1 , 56.
P. G . Rustamov, B. K. Babaev, and R. S. Gamidov, NOD.
Poluprov. Muter., 1972, 65.
G. D. Guseinov, F. M. Seidor, Kh. Ya. Khahlov, and M. Z. Ismailov, Russ. J. Phys.
Chem., 1972,46,466.
J. H. C. Hogg, H. H. Sutherland, and D. J. Williams, Acta Cryst., 1973, B29, 1590.
Ya. Kh. Grinberg, V. A. Boryakova, and V. F. Shevel'kov,J. Chem. Thermodynamics,
1973,5,233.
395
396
3s7
3s8
D. Muller, G. Eulenberger, and H. Halm, Z . anorg. Chem., 1973, 398, 207.

T. J. Isaacs, J. Appl. Cryst., 1973, 6 , 413.
J. Parkes, R. D. Tomlinson, and M. S. Hampshire, J . Appl. Cryst., 1973, 6, 414.
A. M. Lozac'h and M. Guittard, Bull. SOC.chim. France, 1973, 6.
626

has been shown399to give a yield of 85 %, using up to 500 mg quantities of
selenium. The Raman spectra of Tl,CS,, BaCSe,, CS2Se2-, and solutions of
CSi- have been measured,40allowing a reassignment of the earlier i.r. data
to be made.
The crystal structures of the compounds SiPb2S, and SiPb2Se4have been
determined.401 In both compounds the silicon atoms are tetrahedrally coordinated to sulphur or selenium atoms with the bond lengths Si-S = 2.10,
Si-Se = 2.27 A. The structural framework is described as consisting of
trigonal prisms of sulphur or selenium atoms, which form a prismatic tube by
sharing triangular faces. The tubes in turn share edges to form corrugated
sheets, with the unshared edges projecting alternately on each side of the
sheet. Although the structures are similar, different co-ordinations of the
lead atoms are observed. In the sulphide two crystallographically different
lead atoms are present, one with seven-fold co-ordination, the other with
eight. The lead-sulphur distances range from 2.82 to 3.50A. In the compound
SiPb2Se4 both lead atoms are in seven-fold co-ordination, with Pb-Se
distances ranging from 2.97 to 3.54 A.
The i.r. spectra of GeS, GeSe, and GeTe, in the form of amorphous films
and crystals, have been compared.4o2Glass formation in the Ge-Se system has
been investigated?03 Starting from vitreous selenium, it was observed that the
mean atomic volume decreased when the content of germanium was increased. A minimum was observed at the composition GeSe,, rising to a
maximum at GeSe, and decreasing again on addition of GeSe. An X-ray
diffraction study of the structure of vitreous GeSe, (and GeSI,) has shown404
that the atoms which are closest neighbours to each other are covalently
bonded. The structure of black phosphorus has been presented405as a model
for the structures of GeS, GeSe, and GeTe. The observed short interatomic
distances, low near-neighbour co-ordinations, and high covalencies of the
amorphous materials may all be rationalized using the model. The equilibrium
phase diagram of the quasi-binary system Cu,SeGeSe, has been established406by d.t.a. and X-ray analysis. The system contains two, incongruentlymelting, intermediate compounds, Cu2GeSe3and Cu,GeSe,, the latter with a
reversible phase change at 55 "C. A polymorphic phase change has also been
reported407for the compound Cu,SnSe,. The pseudo-binary phase diagram of
the system PbS,-,Se, has been redetermined?O*
300
(0
'02
(03
404
(06
407
Oo8
L. Henriksen and E. S. S. Kristiansen, Internat. J. Sulfur Chem. (A), 1972, 2, 133.

A. Muller, N. Mohan, P. Cristophliemk, I. Tossidis, and M. Drager, Spectrochim.
Acta, 1973, 29A, 1345.
J. E. Iglesias and H. Steinfink, J. Solid State Chern., 1973, 6 , 93.
V. P. Zaknarov and V. S. Gerasimenko, Ukrainfiz. Zhur., 1972, 17, 2073.
A. Feltz and F. J. Lippmann, 2. anorg. Chern., 1973, 398, 157.
Yu. G. Poltavtsev and V. M. Pozdnyakova, Izuest. Akad. Nauk. S.S.S.R., Neorg.
Muterialy, 1973, 9, 853.
A. Bienenstock, J . Non-Crystalline Solids, 1973, 11, 447.
C. Carcaly, N. Chezeau, J. Rivet, and J. Flahaut, Bull. Soc. chirn. France, 1973, 1191.
L. I. Berger, Z. I. Isaev, and E. G. Kotina, Izuest. Akad. Nauk. S.S.S.R., Neorg.
Materialy, 1973, 9, 768.
A. J. Strauss and T. C. Harmon, J. Electronic Muter., 1973. 2 , 71.
627
Group V Element-Selenium Compounds.-The compounds P4Se7,2C5H5N,
P,Se7,2MeC, H,N , P4Se7,3EtC5H4N, P4Se, ,6EtC5H4N, and [C,H,NH+],[HP,Se;-] have been characterized409by elemental analysis and i.r. and mass
spectroscopy. The i.r. study showed absorptions characteristic of the P=Se,
P-Se-P,
and P-N stretching vibrations. The presence of the ions PzSe$,
P,Se& P,Se$, and PSe+ in the mass spectra of the different phosphorus
selenide-amine derivatives reflects the stability of these ions and supports the
proposal that these phosphorus selenidesare structurally similar, both to each
other and to the corresponding phosphorus sulphides. This suggests that the
P4Se, moiety (54) is isomorphous with the well-known P4S7cage.
(54)
Three independent studies4104u of the crystal structure of As,Se4 have

shown, in complete agreement with each other, that the compound is isostructural with a-As4S4and comprises discrete molecules of As4Se4possessing
almost exact 42m (D2J symmetry (55). The average bond lengths and angles
found were As-As 2.56, As-Se 2.39 A, LSeAsAs 101.2', LSeAsSe 94.1',
LAsSeAs 98.1'. The previously reported structure of As,Se, has been
slightly modified,411 with revised parameters for the monoclinic lattice being
a = 4.30,b = 9.94, c = 12.84Ay/I= 109.1', and a mean As-Se distance
40s
C. D. Mickey and R. A. Zingaro, Inorg. Chem., 1973,12,2115.
*lo
T.J. Bastow and H. J. Whitfield, J.C.S. Dalton, 1973, 1739.

A. L. Renninger and B. L. Averbach, Acta Cryst., 1973,B29, 1583.
J. M. Smail and G. M. Sheldrick, Acta Cryst., 1973,B29, 2014.
411
*I2
41
628
of 2.40 A. The structure of As,Se, has been studiedP13in the vitreous state by
X-ray diffraction and in the amorphous state by electron diffraction. Whilst
the composition of the two forms remained the same within 5 % the structures
of the two forms differed considerably. A model was proposed for the
structure of vitreous As2Se3in which unlike atoms are the nearest neighbours
and are arranged in layers. A separate study414has also proposed a model for
the structures of vitreous As,Se, and As,S,. The heats of fusion of some
ternary ABXz chalcogenides (A = Ag or Cu; B = As, Sb, or Bi; X = S or
Se) have been dete~mined.4~~
The kinetics and mechanism of crystallization of
semiconducting, vitreous, A S S ~ ~ , , P alloys
~ , . ~ ~have been studied.416 Phase
M,X-Sb2X3
~~~
diagrams have been studied for the systems A g - - A ~- - S e ,4 ~~8
(M = alkali metal, X = S or Se),419Sb,Se,-GeSe, and Sb,Se3-GeSe,420 and
Sb2Se3-Ti2Se.421Enthalpies of mixing of Bi + Se and Sb + Se in the liquid
state have been measured422and were found to be a maximum at compositions corresponding to Bi,Se, and Sb,Se3. Also reported are enthalpies of
mixing of Tl-Se and TI-S in the thallium-rich region. A new phase of the compound Bi,Se, 11, which is metastable under normal conditions, has been prepared423at high temperature and pressure. The compound, which is isostructural with Sb2S3, has a structure composed of two infinite, zigzag,
-Sb-S-Sb-S
chains. The compound Bi,O,Se has been
to crystallize in the (Nao.2SBi0.,5)202C1
type of structure (space group I4rnrnm
D g ; a = 3.891, c = 12.21 A).
An attempt has been made425to correlate the crystal structures of ternary
chalcogenides of the general composition AB,X4, where X = S, Se, or Te,
with the cationic radius ratio and a pseudo-force constant involving their
electronegativities. The resultant diagram adequately resolves structures
based on many types, but structures based on spinel, Cr3Se4, and Ag,HgI,
are not resolved.
Selenates.-The relative Raman intensities of the vz, v3, and vq fundamentals
of the oxoanions SO:- and SeOi- have been measured426in aqueous solution.
Yu. G. Poltavtsev, V. P. Zakharov, U. M. Pozdnyakova, and T. V. Remizovich,
Izuest. Akad. Nauk. S.S.S.R., Neorg. Materialy, 1973, 9, 907.
414 V. M. Bermudez, J. Chem. Phys., 1972, 57, 2793.
415 R. Blachnik and B. Gather, Z . Naturforsch., 1972, 27b, 1417.
416 E. V. Shkolnikov, Izuest. Akad. Nauk. S.S.S.R., Neorg. Materialy, 1973, 9, 18.
417 S. A. Tarasevich, Z . S. Medvedeva, I. S. Kovaleva, and L. I. Antonova, Russ. J.
Inorg. Chem., 1972, 17, 763.
418 1. S. Kovaleva, Z . S. Medvedeva, S. A. Tarasevich, and L. I. Antonova, Russ. J.
Inorg. Chem., 1972, 17, 1622.
419 V. B. Lazarev, S. I. Berul, and A. V. Salov, Thermal Analysis Proc. 3rd. Internat. Con$,
1971,2, 171.
4z0 G. M. Orlova, I. I. Kozhina, and U. G. Korolenko, Vestnik Leningrad. Univ., Fiz.
Khim., 1973, 90.
431 A. Gaumann and P. Bohac, J . Less-common Metals, 1973, 31, 314.
422 T. Maekawa, T. Yokokawa, and K. Niwa, J. Chem. Thermodynamics, 1972, 4, 873.
423 E. Ya. Atabaeva, S. A. Mashkov, and S. V. Popova, Soviet Phys. Cryst., 1973,18,104.
4 2 4 H. Boller, Monatsh., 1973, 104, 916.
425 J. E. Iglesias and H. Steinfink, J. Solid State Chem., 1973 6 , 119.
426 H. Schulze, N. Weinstock, A. Muller, and G. Vandrish, Spectrochim. Acta, 1973,
29A, 1705.
413
629
1.r. spectra of SO:- and SeOi- in host lattices of salts of alkali and alkalineearth metals with other oxoanions have been measured427and a discussion
of the interaction between the host lattice and the substituted anion has been
published. The chemical forms of 75Segenerated by thermal neutron irradiation, and by implantation of 75Seions in K2Se04crystals,have been
The results of the study suggest that the main species generated by neutron
capture in the alkali-metal selenates result from the loss of 0-rather than of
02-or 0. The rate of oxygen exchange between ele en ate^^^ and selenite430
ions and water has been measured using oxygen-18 tracer methods.
The Raman and i.r. spectra of (NH4),Se04, (ND4),Se04, and Li(NH4)Se0,
have been recorded431at 300 K. Crystals of (NH4),Se04 exhibited some 33
Raman lines while Li(NH4)Se04 showed 30 Raman lines. The SeOi- ions
and the NH$ ions are highly distorted in these compounds and a lowering of
the N-H vibrational frequencies due to hydrogen-bonding was observed.
The solubility of Na,SeO, in several organic solvents at varying temperatures
has been determined and the specific gravity of the solutions measured.432
The behaviour of the hydrate Na,SeO,,lOH,O in the same solvents showed
that dehydration to Na,SeO, takes place in MeOH and EtOH but is incomplete in PrnOH and acetone. The crystal structure of sodium ammonium
selenate dihydrate, NaNH4Se04,2H,0, has been established by X-ray
diffraction?33 The positions of the hydrogen atoms were unambiguously
determined by the n.m.r. spectra of l H and 2Hin the partly deuteriated
crystal. The structure comprises very regular SeO, tetrahedra, with a mean
selenium-oxygen distance of 1.62 A, linked by sodium atoms along the
crystal c-axis. The bands of tetrahedra are cross-linked by NH, groups and
hydrogen bonds to form a three-dimensional structure. D.t.a., t.g.a., and Xray
of the thermal degradation of Na6H4(Se0,),,4H,0 showed the
sequence of reactions of Scheme 2 to take place. The first determination of
the structure of a compound in the series K,Mr1(Se04),,2H,0 has been carried
The compound K,Cd(SeOp),,2H,0 crystallizes in the space group PI,
with the dimensions a = 7.539, b = 6.631, c = 11.494 A; a = 71.8',
= 83.9, and y = 109.9'. Hydrogen bonding was found to be rather weak in
this compound.
The indium(ru) selenate In,(Se04),,9H,0 has been prepared436by dissolving freshly precipitated indium hydroxide in dilute selenic acid. Thermal
427
428
429
430
431
431
43 3
434
436
436
H. J. Becher, F. Friedrich, and H. Willner, 2.anorg. Chem., 1973,395, 134.

M. Cogneau, G. Duplatre, and J. I. Vargas, J. Inorg Nuclear Chem., 1972, 34, 3021.
A. Okumura and N. Okazaki, Bull. Chem. Soc. Japan, 1973, 46, 1080.
A. Okumara and N. Okazaki, Bull. Chem. SOC.Japan, 1973, 46, 1084.
V. N. Sankaranarayanan and R. S. Krishnan, Proc. Indian Acad. Sci., Sect. A , 1972,
76,267.
M. Manewa and M. Stoitschewa, Monatsh., 1973,104, 356.
A. I. Kruglik, V. I. Simonov, and V. I. Yuzvack, Soviet Phys. Cryst., 1973,18, 177.
N. M. Selivanova and L. G. Slobol, Izvest V.U.Z., Khim. i khim. Tekhnol., 1973, 16,
331.
S . Peytavin, E. Philippot, and 0. Lindquist, Cryst. Struct. Comm., 1973, 2 , 163.,
E. N. Deichman, I. V. Tananaev, and N. V. Kadoshnikova, Russ. J. Inorg. ChemJ972,
17, 16.
630
155 "C
Na6H4(Se04)6,4Hz0--+ Na,H,(SeO&
+ 4H20
J220 "C
+ NazSeO, + Na,Se,O,
NaHSeO,
1300
rhombic Na,SeO,
J555 "C
hexagonal Na,SeO,
oc
Na2Se04 Na,Se,O,
SeO,
Ogcl 450C
-730
* "0
Na,SeO, liquid
Scheme 2
analysis showed that decomposition of the compound takes place in the

following endothermic stages :
In,(Se0J,,9H20
130 "C
__+
185 "0
In2(Se0Ja,5H,0
150 "C
-*
325 O
In2(Se0,),,3H20 _ _ j In,(Se0J8,2H,O p
.
In,(Se03,,4H20
In,(SeOJ,,H,O
InzOa SeO,
175 "C
+
-.
550-635 "C
-
+ 0, + H 2 0
The formation of the monohydrate at 325OC is accompanied by a partial

reduction of SeV1 to SeIV. The In2(Se04),-H2Se0,-H20 system has been
studied437and the formation of the compounds In2(Se04),,8H20,In2(Se04)3,
H2Se04,9H20,and In2(Se04)3,2H,Se04,9H20established.
The thermal decomposition of the double salt (NHJ2Mg(Se04),,6H20 has
been
to take place in the following sequence:
The compound Cs,Mg(Se04),,6H,0 has been shownPSgto lose water endothermically at 128, 160, and 250 "C to form the tetrahydrate, dihydrate, and
amorphous C S , M ~ ( S ~ Orespectively.
~)~,
Crystallization, melting, and partial
reduction of Cs,Mg(SeO,), occurred at 308, 560, and 620 O C , respectively.
The thermal decomposition of the sodium acid selenates NaHSeO, and
437
438
q3g
E. N. Deichman, I. V. Tananaev, and N. V. Kadoshnikova, Russ. J. Inorg. Chem.,

1972,17, 117.
N. M. Selivanova, L. A. Prymova, L. Kh. Krauchenko, and V. T. Orlova, Russ. J .
Inorg. Chem., 1972, 17, 801.
L. A. Pyrmova, N. M. Selivanova, and Yu. M. Khozhainov, Izoest. V.U.Z. Khim. i
khim. Tekhnol., 1972, 15, 1775.
63 1
Na&&(Se04)5 has been showna0 to take place according to the following
sequences:
2NaHSe0,
NarHs(SeO.),
- 21O-27O0C
Na,Se,O,
440 "C
Na,SeO,
+ SeO, + A03
F 4NaHSe0, + SeO, + *O, +
170-200 "C
2Na,Se,O,
330 O
+ 2Ha0
440 "C
____f
2Na,SeO,
Se1enites.-Nuclear transformations in solids do not usually lead to oxidation

of the affected atornyM1but a system has now been described with an anionic
target species in which the annealing reaction does lead to an oxidized species
and not to the target substance.a2 The neutron irradiation of hydrated, or
anhydrous, sodium selenite leads to the formation of radioactive elemental
selenium, selenite, and selenate. On thermal annealing the proportion of
elemental selenium decreases and that of selenate increases, with the selenite
showing little change. Since there seems no reason to doubt that the SeO
fraction represents atomic selenium in interstitial or abnormal lattice sites,
the observed process must be due to a reaction between Seo and selenite ions
or the reaction of SeO with oxidizing fragments produced by the recoil event
in the lattice.
0 a-
l--se<J
+
SeO,
4-
[o>e-o]
+ 2Se0-
Lithium hydrogen selenite has been preparedM3in 95% yield by neutralization of a selenious acid solution with LiOH to pH 4-45.
The ferroelectric compound NaD,(Se03), has been
to have a
monoclinic crystal structure with a = 5.787, b = 4.844, c = 11.794 A and
fi = 118.4' in the space group P2,/c. The selenium atom in the selenite ion is
0.77w from the plane of the oxygen atoms and does not have ideal 3m
symmetry. The three oxygen atoms covalently bonded to selenium are accompanied by a further three oxygen atoms at a distance of 3.4& thus
forming a distorted octahedron. The rubidium hydrogen selenite RbH3(Se03),
~ r y s t a l l i z e in
s ~an
~~
orthorhombic
~~~~
unit cell with a = 5.9193, b = 17.9506,
and c = 6.2519 A in the space group P2,2,2,. The structure consists of two
types of chains at right angles. One chain is built up of H2Se03 molecules
linked by hydrogen bonds of length 2.594 A, and the other of HSe0; ions
L. G. Sobol and N. M. Selivanova, Russ. J. Inorg. Chem., 1973,18, 323.
F. R.AlSiddiqui and A. G. Maddock, J . Inorg. Nuclear Chem., 1972,34, 3007.
442 F. R. Al-Siddiqui, A. G. Maddock, and T. Palma, J . Inorg. Nuclear Chem., 1972,34,
3015.
4c3 E. M. Shipilova and T. V. Revzina, Metody. Poluch. Khim. Reactiv. Prep., 1972, No.
24, p. 59.
p44 J. K. Mohana Rao, Soviet Phys. Cryst., 1972, 17, 432.
R. Tellgren, D. Ahmad, and R. Limingen, J. Solid-State Chem., 1973, 6 , 250.
44Q
441
632
linked by hydrogen bonds of length 2.571 A. The two chains are cross-linked
by a third hydrogen bond of 2.521 A. The structure of NH,H3(Se03), has
been
to be similar to that of RbH3(Se03),, with rigid polar (SeO;-)I
and (SeO$-)II groups linked by a three-dimensional hydrogen-bonded system.
The dielectric properties of LiD3(Se03), have been in~estigated.4~~
The
hydrogen-bonding network in KH3(Se03), has been studied by neutron
diffraction449and the results of earlier X-ray work have been confirmed.
The Raman and i.r. spectra of the ferroelectric compounds LiH,(Se03),
and NaH3(Se03), and of the antiferroelectric KH3(Se03), have been rec0rded.4~~
The spectra were interpreted in terms of HSe03 and H,Se03
vibrations in LiH3(Se03)2and NaH,(SeO,), (below the transition temperature), and in terms of H3Se0$ and SeOg- for the low-temperature spectrum of
KH,(SeO,),. An earlier
of the Raman and i.r. spectra of KH3(Se03),
analysed the spectra in terms of HSe03 and H,Se03 groups below the
transition temperature. The Raman and i.r. spectra of Na,Se03, NaHSeO,,
NaH,(SeO&,, and H2Se03 have been measured452and compared with the
solution Raman spectra of SeOi-, HSeOy, and H,Se03.
The thermal behaviour of NaHSeO, in neutral atmosphereshas been studied
and shown to follow the sequence:453
NaHSeO,
120-130 "C
"C
+ NazSezOs 380-400
+ Na,Se,O,
(liquid)
J.700""c+ SeO,
Na,SeO,
The dehydration and dissociation of BeS03,4H,0 has been investigated.454

Loss of water takes place in two stages at 120 and 260 "C;crystallization of the
salt at 340 OC is followed at 485 O C by decomposition, with the release of SeO,
into the gas phase and the formation of Be0 as the final solid phase:
BeS02,4H,0 -+ B e 0
+ SeO, + 4Ha0
The dissociation pressures of Bi,(SeO,)s at 442-612 "C and Bi,03,Se0, at

513-596 "C have been measured.45sThe compound Bi20,,Se02 was found
to be stable between 300 and 450 O C .
446
447
*48
449
450
451
452
453
454
piis
A. B. Tovbis, T. S. Davydova, and V. I. Simonov, Soviet Phys. Crysf., 1972,17,81.

L. V. Gorbatyi, V. I. Ponomarov, and D. M. Kheiker, Soviet Phys. Cryst., 1973, 17,
1002.
L. A. Shuvalov, V. N. Anisimova, N. R. Ivanov, and I. A. Velichko, Souief Plays.
Cryst., 1973,17, 1096.
B. Prelesnik and R. Herak, Acra Cryst., 1972,B28, 3104.
P. K. Acharya and P. S. Narayanan, Spectrochim. Acta, 1973,29A,925.
P.K.Acharya and P. S. Narayanan, Indian J. Pure Appl. Phys., 1972,10, 827.
B. H.Torrie, Canad. J . Phys., 1973,51, 610.
V. G. Shkodin, G . L. Akhmetova, and S. K. Akhmetov, Izvest. Ucheb. Zaved. Tsvet.
Met., 1973,104.
M. I. Berezina, V. V. Pechkovskii, and G. F. Pinaev, Russ. J. Inorg. Chem., 1972, 17,
931.
S. S. Bakeeva, A. S. Pashinkin, and M. I. Bakeev, Tr. Khim. Met. Ins?. Akad. Nauk.
Kazakh. S.S.R., 1972, 19, 130.
633
Normal and acid scandium selenites have been prepared from aqueous
solutions and their solubilities in H 2 0and H2Se03
The thermal
decomposition of Sc2(Se0,),,5H20 may be represented by the sequence:
The decomposition of Sc(HSeO,), may be given as:
Sc,O,,SeO,
740 O C
+ SC,O,
-SeO,
Both Sc2(Se0,),,5H20 and Sc(HSeO,), undergo slight reduction of Se4+to

red elemental selenium and yellow-orange intermediate products when heated
in the range 200-600 "C.
The reduction of selenite ions by some selenothionate and thiosulphate ions
has been studied. Se0;- reacts457with SeS,Oi- in acidic solutions to form
selenanemonosulphanedisulphonateswith <6 Se atoms in the chain. The
ions Se,S,Oi- and Se,S,Oq- were detected for the first time. SOf- and
SeS,Oi- reduce SeOg- in acidic solutions to selenium metal but selenanedisulphonates are produced as intermediate products.458In neutral systems,
species exist with <4 Se atoms in the chain; in acidic solutions species with
9 7 Se atoms in the chain were formed, including the new species Se,S,Oi-.
Selenium metal is precipitated by the decomposition of the longest-chain
intermediates. SeOg- reacts with S,Og- to form SeS40i- and S40i-.459Excess
S20g- reacts with SeS,O;- in neutral solutions to form SeSSOg-, which decomposes to selenium. In acidic solutions, this reaction is of less importance,
and only minor precipitation of selenium is observed; instead a sequence of
build-up reactions takes place.
Other Compounds of Selenium.-Several methods for the synthesis of triselenadiborolans (56) and the structure and formation of the cyclic fivemembered ring have been
The reaction of R2BX (X = I or H)
456
A. S. Znamenskaya and L. N. Komissarov, Russ. J . Inorg. Chem., 1973,18, 458.
457
E. Blasius and A. Knocchel, J. Radioanalyt.

E. Blasius and A. Knoechel, J. Radioanalyt.
E. Blasius and A. Knoechel, J. Radioanalyt.
W. Siebert and F. Riegel, Chem. Ber., 1973,
458
459
c60
Chem., 1973, 13, 373.

Chem., 1973, 13, 363.
Chem., 1973, 13, 381.
106, 1012.
634
with selenium yields the hitherto unknown diboryl selenanes, which decompose on heating to form the five-membered ring, selenium, and R,B. Replacement of the Se, bridge in the ring by NW-dimethylhydrazine leads to the formation of the new B-N-Se heterocycle (57). The Se, bridge is, however,
maintained in the reaction to produce (57a). The preparation and chemical
Se- Se
RB
e,\/
BR
RZNHz +RIB
R = Pr,R2
= Ph
Se-Se
BR1
R2
(574
reactivities of S,N4, (Sew,, and (TeN), have been

N2H4adsorbed
on active SiO, acts as a reducing agent on S4N4,to give S,NH together with
some 1,3-S6(NH)2 and 1,3,5-S5(NH),; The nitrides of Se and T1 were found
to decompose when the same reducing agent was added to solutions of the
nitrides in CCl,. Halogenation reactions using AgF and Br in CCI, solution
yield Br4S,N4 and F4S,N4with the sulphur nitride, (NH4),SeBr6being formed
on bromination of (SeN), in CCI,. The reaction of SOC1, with S,N, gives
chlorinated cyclic compounds and S4N3CI, whilst (SeN), yields (NH,),SeCI,(S0)2.
The i.r. spectra of some clathrate compounds of hydroquinone with H2S,
EI,Se, D,S, and D,Se have been studied and three new absorption bonds
observed.462The vacuum-u.v. spectra of the transient diatomic species HSe
and HTe have been observed463following the isothermal flash photolysis of
IIzSe and H2Te, respectively. Rydberg series leading to the first ionization
potentials suggest the values I.P.(HSe) = 9.8 eV and I.P.(HTe) = 9.1 eV.
The extraction of selenous acid by mono-, di-, and tri-octylamines has been
H . Garcia-Fernandez, Bull. SOC.chim. France, 1973, 1210.
X. Gerbaux, C. Barthel, A. Hadni, and M. M. Pradhan, Spectrochim.Actu, 1973,
29A, 1695.
R. J. Donovan, D. J. Little, and J. Konstantatos, J.C.S. Furuduy 11, 1972, 68, 1812.
461
462
463
635
studied by two-phase titration and partition meth0ds.4~~
The equilibrium
constants for the reaction of selenous acid with solutions of the primary,
secondary, and tertiary amines in octane were found to be 6.2 x lo5,
7.07 x lo4, and 1.4 x lo2, respectively.
The reaction of (Me,N),SeO or (RO),SeO with NH,, MeNH,, and
H,N(CH,),NH, has been
to give the amides of the selenious acid,
(NH,),SeO, (MeNH),SeO, and (CH,NH),SeO. The compounds are stable
only at low temperatures. A series of compounds of the general formula
M','P2& (X = S or Se) have been prepared by reaction of the stoicheiometric
mixtures of the elements at elevated t e r n p e r a t ~ r e s .According
~~~
to X-ray
analyses these compounds are best classified as hexathio- or hexaselenohypodiphosphonates. The reaction of seleno- and telluro-polythionates with
SPOZ- has been
to give SeS,P,O!" and TeS,P,O!-:
The synthesis and properties of neutral chelates of the new ligand NNdimethylthioselenocabonate with the tripositive ions of Ga, In, and T1 have
been
Trischelates were obtained for the 3 + ions and a 1 : l
chelate (58) for TI'. X-ray photoelectron spectra have been determined469
for cyanate, thiocyanate, selenocyanate, and tellurocyanate ions in the

compound PhAs'NCX- (X = 0, S, Se, or Te).
4 Tellurium
The Element.-The
structure, preparation, and physical properties of
tellurium have been reviewed.470A method for the purscation of tellurium to
A procedure for the estimation
a purity of 99.99995 % has been de~cribed.4~~
464
465
466
467
468
469
470
471
G . P. Giganov, A. M. Tserekova, and R. I. Prikhod'ko, Russ. J. Inorg. Chem., 1972,

17, 102.
G. Hopf and R. Paetzold, 2.anorg. Chem., 1973, 401, 179.
W. Klingen, R. Ott, and H. Hahn, 2.anorg. Chem., 1973, 396, 271.
E. Blasius and N. Spannhake, 2.anorg. Chem., 1973, 399, 331.
R. Heber, R. Kirmse, and E. Hoyer, 2.anorg. Chem., 1972, 393, 159.
A. H. Norbury, M. Thompson, and J. Songstad, Inorg. Nuclear Chem.Letters, 1973,9,
347.
W. Becker, V. A. Johnson, and A. Nussbaum, Tellurium, 1971, 54.
B. Schaub and C. Potard, Proc. Internat. Symp. Cadmium Telluride, Muter, GammaRay Detectors, 1971 (published 1972) 11-1.
636

of tellurium in nanogram quantities by atomic absorption has been given472
and the interference of Te in the estimation of copper in selenium by diethyldithiocarbamate may be avoided by oxidizing Te4+to Te6+with K2Cr,07.473
The atomic chain structure of Te-Se alloys containing 1.6-100 atom % Te
has been in~estigated.~'~
The results indicate that, even at low concentrations
of tellurium in the alloy, the tellurium atoms are distributed in groups of
several atoms. The solution calorimetry of tellurium and selenium in liquid
bismuth has been studied.475The heat of solution of Te in liquid bismuth was
determined as -1.16 f 0.07 kcal mol-l at 635 K. The enthalpies of solution
of several cuprous selenides were measured and enthalpies of formation
calculated. The 125Te Mossbauer spectra of a number of TeII and TeIV
complexes with thiourea and related derivatives have been mea~ured.4~~
The
isomer shifts and quadrupole splittings for several of the compounds were
interpreted in terms of a bonding scheme utilizing three-centre, two-electron
bonds in which Te 5p electrons participate.
Tellurium-Oxygen Compounds.-Two new phases with the formulae H2Te,06

and Te40Qhave been prepared477by hydrothermal synthesis in the form of
single crystals. H2Te,0, crystallizes in the orthorhombic space group Pna2, ,
with the cell constants a = 12.067, b = 8.037, and c = 4.735 A, whilst
Te,OQ crystallizes as rhombohedra1 crystals in the space group P3, or P32,
with the hexagonal cell constants a = 9.32 and c = 14.48 A. The behaviour
of TeO, and SeO, in disulphuric acid has been s t ~ d i e d . 4TeOz
~ ~ is solvolysed
in H2S207to give H,Te(HSO,),, which behaves as a weak acid:
TeO,
+ 8H2S207
H SO,
+ H[Te(HSO,),]- + 3HaS,01,
SeO, behaves as a weak base with a tendency to polymerize at higher concentrations :

Se02
2H&07 += SeO+OH
HS,Oy0
HaSOd
The reactions of K2C03and Rb2S03with TeO, to form the corresponding

compounds M2Te03, M2Te,0S, and M,Te,O, have been followed by d.t.a.479
A study of the Bi,O,-TeO, system at 450 "C has shown4s0the following four
phases to be formed: Bil6Te@,p, an orthorhombic solid solution with the
limiting compositions Bi2Te06 and Bi2Te207,BiloTe2019, and Bi,Te4OI1.
Single crystals of the oxide Te20Shave been prepared by hydrothermal
473
474
475
476
477
478
470
480
R. D. Beaty, Analyt. Chem., 1973, 45, 234.

S. N. Ranade and N. S. Kunte, Indian J. Chem., 1972,10,949.
0 . Vaiciuliene and K. Makariunas, Phys. Status. Solidi (B), 1973, 55, K35.
K. G. Skeoch and R. D. Heyding, Canad. J. Chem., 1973, 51, 1235.
B. M. Cheyne, C. H. W. Jones, and P. Vasudev, Canad. J. Chem., 1972, 50, 3677.
J. Moret and 0. Lindqvist, Compt. rend., 1972, 275, C, 207.
K. C. Malhotra and R. D. Sharma, Indian J . Chem., 1972, 10,430.
V. I. Mazepova, K. K. Samplavskaya, and M. Kh. Karapet'yants, Zzvest. Akad. Nauk.
B. Frit and M. Jaymes, Rev. Chim. minkrale, 1972,9, 837.
637
synthesis and the crystal structure has been determined.481The crystals are
monoclinic in the space group P2,,with the cell constants a = 5.368, b =
4.696, c = 7.955 A, and B = 104.82'. The oxygen co-ordination of the
tellurium atoms provides clear evidence that Te,O, contains tellurium in both
the IV and VI oxidation states. TeV1 was found to have the usual octahedral
co-ordination, as in %(OH),, while the co-ordination of TeIV was irregular
four-fold, being similar to that found in a-and @-Te02.Tevl-O and TeIV-O
distances are in the ranges 1.848-1.972 and 1.892-2.080 A, respectively.
The crystal structure of KTeO,(OH) has been reinvestigated.482The compound crystallizes in the space group P2,/a, with a = 6.498, b = 11.969,
c = 5.121 A, and /I= 93.86'. The structure contains TeO, octahedra sharing
edges, thus forming infinite chains. Apart from the electrostatic forces due to
the potassium ions, the [TeO,(OH)]g- chains are held together by strong
hydrogen bonds with distances of 2.480 A. The co-ordination distances around
the tellurium atom are: Te-O(bridge) 1.945, 1.947, 1.994, and 1.997 A;
Te-OH 1.883 A; and Te-O(termina1) 1.843 A.A neutron-diffraction study
of the monoclinic modification of telluric acid Te(OH), has been carried
in order to obtain the hydrogen positions to high accuracy. Analysis of
the Te-0 bond distances suggests that the hydrogen bonds in the structure
may cause deviations from the ideally octahedral co-ordination of oxygen
around the tellurium atom. That this is the case is clearly indicated by the
significant deviations of the OTeO bond angles from 90".
Single crystals of H,Te,O, have been prepared by hydrothermal synthesis
and a crystal structure has been
The compound crystallizes in
the space group Pbn2i, with the cell dimensions a = 8.037, b = 12.070, and
c = 4.735 A. The structure contains TeVIO, octahedra and four-co-ordinate
TeIV units, with the bond distances TeV1-O in the range 1.864-1.952 A
and TeIV-0 in the range 1.861-2.107 A. The Tevl octahedra are linked
through corners to form chains which are connected via TeIV-0 chains of the
\/
type -Telv-O-Telv-O-
to form infinite sheets. The sheets are held
/\
together by hydrogen bonds and van der Waals forces only, thus resulting in
a cleavage plane in the crystals. The H,Te,O, structure is closely related to that
of Te,O,, the three-dimensional structure of which may be regarded as a
condensation of H2Te206layers.
The reactions of sodium tellurite and potassium tellurite with monosulphide
sulphur in alkaline solution have been in~estigated.4~~
Stepwise complex
formation was observed in the TeOg--S2--OHand TeOi--S2--OHsystems. Thio-salts of TeIV with less than 3 ligands were found to be unstable
and to disproportionate into tellurite and trithiotellurite ions. The most
481
482
483
484
485
0. Lindqvist and J. Moret, Acfa Cryst., 1973,B29, 643.

0.Lindqvist, Acfa Chern. Scand., 1972, 26,4107.
0. Lindqvist and M. S. Lehmann, Acfu Chern. Scand., 1973, 27, 85.
0.Lindqvist and J. Moret, Acfu Cryst., 1973, B29, 956.
T.N. Greiver and Yu. A. Zaitsev, Russ. J . Inorg. Chem., 1972,17,796.

638
stable of the thio-salts of TeV1 were the oxomonothiotellurate and tetrathiotellurate species,
to crystallize in the space group
The compound CuTe,05 has been
P2i/c, with the cell constants a = 6.871, b = 9.322, c = 7.602 A, and =
109.08". The structure comprises a three-dimensional net, resulting from
copper and tellurium co-ordination polyhedra sharing oxygen atoms. Each
oxygen atom interacts with three metal atoms, two of the interactions being
strong and one weak. Both crystallographically independent tellurium atoms
have three strong pyramidal bonds to oxygen (59), with Te-0 distances in
\/
oLTe(1)
*'\
0'
the range 1.859-2.019 A, and in addition, one of them has a fourth interaction with oxygen [Te(2)-0' = 2.402 A] whilst the other has two weaker
bonds with distances Te(1)-0' of 2.607 and 2.733 A.
Microcrystals of the compound Li4Te207have been prepared487by heating
Li,TeO, under vacuum at 580C. Heating Li,Te20, in air gives Li,Te04
at 555-600 "C and Li2Te03at about 750 O C . Crystallographic parameters of
the triclinic cell of Li4Te,0, were determined.
Depending on the conditions used, the hydrolysis of normal strontium
orthotellurate can yield the tetrahydro-orthotelluratein either crystalline or
amorphous forms.488The behaviour of the amorphous salt on heating in the
range 100-1 100 "C may be represented by the following sequence of compounds:
SrH4TeOi3
80-170 "(3
--H,O+ SrHaTeO,
290-500 "C
____+
-H,O
SrTeO, (amorphous)
370-800 "C
SrTeO, (crystalline) + SrTeO, (solid)
530-570 'C
-
980
f
O C
-+02
SrTeO, (liquid)
1010 '
C
~
SrO
+ TeOa
The reactions of aqueous solutions of tellurite, selenite, and arsenite with

H,Te result489in rapid isotopic exchange with tellurite, and rapid reduction to
H2Se and ASH,, respectively.
486
R. Hanke, V. Kupcik, and 0. Lindqvist, Acta Cryst., 1973,B29,963.
487
J. Moret, A. Norbert, and D. Cachau-Herreillat, Compt. rend., 1973,276,C,677.
488
R. N. Knyazeva and G . S. Zhuravleva, Russ. J . Inorg. Chem., 1972,17,415.

L. Tomlinson and M. H . Hurdus, Radiochim. Acta, 1972, 17, 199.
48B
639
Tellurium-Halogen Compounds.-The first investigation of the structures of
the recently prepared tellurium subhalides TeyX (X = C1, Br, or I, y > 1)
has been reported.490The building unit of Te,CI, is shown in Figure 8; an
infinite tellurium screw, such as is present with a simpler conformation and
higher symmetry in elemental tellurium, is observed. Each third Te atom
100.5
2.68
3.1 8
3.09
286
289
927
2.8 6
29. 2
254
103.6
7 28
1u1.4
92.2
91.0
9 6.5
1006
93.2
92.6
8a9
83.9
83.9
I
Figure 8 Building units of Te3C12(left) and Te,X (right); bond IengthslA and
bond angles/". The data for Te2X are those for Te,I
binds two CI atoms axially, thereby giving the composition Te3Cl,. Figure 8
also shows the macromolecular structural unit of the Te,X type. Here also,
a skeleton of Te atoms lies parallel to the crystallographic c-axis, this time
with bridging halogen atoms on the edges.
Crystallographic data for the subhalides of tellurium are given in Table 2.
Phase investigation^^^^ have shown the Te-TeC1, and Te-TeBr, systems to
be of the pseudo-binary, peritectic type with the phases Te3CI, and Te,Br,
respectively. TeCI, and TeBr, do not exist as stable crystalline phases under
normal conditions. The reduction of solutions of TeCI, with elemental
R. Kniep, D. Mootz, and A. Rabenau, Angew. Chem. Internat. Edn., 1973, 12, 499.
A. Rabenau and H. Rau, 2. anorg. Chem., 1973, 395,273.
640
Inorgarlic Chemistry of the Main-group Elements
tellurium in KAlCl, melts buffered with KC1-ZnCl, has been shown492to

yield initially Te2+and finally the solvated entity Teg+. The vibrational spectra
of MeTeCl,, Me2TeC1,, and MeTeClg have been reported and the values of
the frequencies of the most intense metal-chlorine stretching mode in the
Raman spectrum compared with those of related compounds.493In the fiveco-ordinate, trigonal-bipyramidal species LMClz-, it is suggested that M-C1
Table 2 Tellurium subhalides: crystallographic data
8.651
100.86
12.81
7.075
4.00
P2Jn
Te,C1
10.137
14.82
Pnarri
Te2Br
14.922
12.842
4.004
Pnam
Te21
15.294
13.694
Pnam
TeI
9.957
104.38
15.384
7.991
90.13
4.179
128.09
4.123
8.214
102.91
12.001
-
PI,P i
C2, Cm
16
Te,CI,
TeJ
C2/m
bonds, in the same equatorial plane as a lone pair or a methyl group, will be
shortened relative to those in the linear MCl, residue. On the basis of such
ideas, predictions were made about the acceptor properties of several species;
for example, Me,TeCl, is expected to have extremely weak acceptor properties. The reaction of BrF, with TeO,, in the temperature range 100-450 "C,
has been found494to yield the volatile products Te3F1402,TeF,, Te2Flo,and
TeF,. The transport of 131Te in a chlorine-oxygen gas stream has been
studied.495The final products of the transport reaction are TeCl,, TeOCl,, or
TeO,, depending on the ratio of chlorine to oxygen employed.
An inve~tigation,~~
of the electron-acceptor properties of TeCl, with some
donor molecules (sulphides, ethers, ketones, and sulphoxides) has been
carried out. Enthalpies of formation and dipole moments of the complexes
were measured and the heats of the reaction:
#Max6
+ TeCI, % TeC14,MX8
for MX, = AlBr,, GaBr,, and GaCl, obtained. Electrical conductivity

measurements of solutions of the complexes in benzene indicate that no free
492
493
484
495
496
N. J. Bjerrum, Znorg. Chem., 1972, 11, 2648.

I. R. Beattie, F. C. Stokes, and L. E. Alexander, J.C.S. Dalton, 1973, 465.
T. Sakuri, J . Nuclear Sci. Technol., 1973, 10, 130.
H. Steinwandter, Inorg. Nuclear Chem. Letters, 1972, 8, 1047.
M. E. Peisakhova, I. P. Goldshtein, E. N. Guryanov, and K. A. Kocheshkov, Doklady.
Chem., 1972,203,372.
641
ions were present , and consequently equilibria of the type :
TeCl,,D 1[TeC18,D]+ C1TeCl,,MX, 1 [TeCl,]+

[MX,Cl]-
do not exist. A studyqg7of the reactions between a-Me,TeCI, and BCI,,

or-Me,TeCl, and BBr,, a-Me,TeBr, and BCl,, TeCl, and BBr,, and TeBr,
and BBr, showed no evidence for the formation of M - + A bonds, where
M Te or Se and A = BCI, or BBr,.
The crystal structure of the 1:1 adduct TeCI,,PCl, has been determined.498
The compound crystallizes in the orthorhombic space group Ima2, with
Figure 9 The polymeric anion (TeClg),

(Reproduced by permission from 2. anorg. Chem., 1973,397, 1)
a = 16.656, b = 12.435, and c = 12.097 A. Besides isolated PCl$ cations

with nearly ideal Tdsymmetry, the structure (Figure 9) contains chain-like
polymeric (TeCI;), anions with distorted octahedral co-ordination of the
tellurium atoms. The polymeric chains consist of TeCI, groups, with C,, symmetry and bond distances Te-ClaXial = 2.489-2.498 A, Te-Clequatorial 2.345-2.382 A, linked by two additional bridging chlorine atoms in cispositions (Te-Clbridge = 2.693-2.852 &. In the series TeCI~--PCl~TeCI;;TeCl,-TeCl$AlCl~-TeCl$AsF~,an increasing steric activity of the inert
electron pair is observed.
Equilibrium diagrams for the systems CsCl-KCl-TeCI, and CsCI-RbClTeCl, ,499 CC1,-TeCl, and GeC1,-TeCl, ,,0 and alkali-metal bromide
TeBr,601 have been studied.
When a solution of equimolar amounts of tellurium(1v) chloride and
triphenylmethyl chloride in benzene is warmed gently, a dark brown solution
498
M. T. Chen and J. W. George, J. Inorg. Nuclear Chern., 1972, 34, 3261.

B. Krebs, B. Buss, and W. Berger, Z . anorg. Chem., 1973, 397, 1.
V. V. Safonov, B. G. Korshunov, and 0. S. Tsyganova, Rum. J . Inorg. Chem., 1972,
17, 906.
V. V. Safonov and A. V. Konov, Russ. J. Inorg. Chem., 1972,17, 1766.
V. A. Grinko, V. V. Safonov, V. I. Ksenzenko, and B. G. Korshunov, Russ. J. Inorg.
Chem., 1972,17,910.
642
is formed from which yellow-brown crystals having the composition Ph,CTe,Cl,, may be isolated.502A complete X-ray analysis has shown that the novel
T e 3 C 1 ion
~ is, in fact, structurally a fragment of the cubane-type compound
(TeCI,),, from which a TeCl; group has been cleaved by a C1- ion functioning
as a Lewis base. The Te3C1~
ion (Figure 10) consists of three distorted TeCI,
Figure 10 Te,CIl3 ion in the triphenylmethyl salt with bond lengths (in A,
standard error 0.005 A) and bond angles (averaged over chemically
equivalent angles)
octahedra, joined via edges to give a trigonal unit with idealized C,,symmetry.
The crystal structure of Rb,TeCl, has been determined503and the data have
been interpreted in terms of a regular octahedral [TeCI,I2- anion with a
Te-Cl bond length of 2.541 A. Lattice-energy calculations on the resulting
structure are reported and are found to be sensitive to the assumed charge
distribution within the anion. The measured heats of solution of TeC1, and
Rb,TeCI, in HCI allowed the standard heat of formation of Rb2TeC1, to be
calculated as -294.4 kcal mol-l at 298 K. The n.q.r. 35Clspectra of 14 salts of
TeClt- have been recordedso4in an effort to observe possible differences in
anion distortion which could result from the inert pair of electrons of TeIV.
No evidence of stereochemical activity of the inert pair was, however, observed. The compounds Cs2TeBr, and Rb,TeBr, have been found505to form a
continuous series of solid solutions with a minimum at 630 "C at 88.9 wt. %
603
604
605
B. Krebs and V. Paulat, Angew. Chem. Internal. Edn., 1973, 12, 666.
M. Webster and P. H. Collins, J.C.S. Dalton, 1973, 5 8 8 .
T. B. Brill and W. A. Welsh, J.C.S. Dalton, 1973, 357.
G. M. Serebrennikova, V. V. Safonov, G. R. Allakhverdov, V. A. Grinko, B. D. Stepin,
and V. 1. Ksenzenko, Russ. J . Inorg. Chem., 1973, 18, 78.
Elements of Group V l
643
Rb,TeBr6. The reaction of H,TeBr6 with several amines in acetic acid has
been shown5Osto give compounds of the type L,H,TeBr, and L4H,TeBr,. The
chemical composition and solubility of the products were studied in different
solvents.
The crystal structure of the compound C4H,STeBr, has been determined.607
The co-ordination around the tellurium atom is that of a distorted octahedron
(60). The two Te-C bonds with distances of 2.14 and 2.16 A make a CTeC
Br
Br
angle of 99.4". Approximately perpendicular to the C-Te-C

plane,
tellurium forms axial bonds to bromine atoms at 2.657 and 2.689 A, with a
BrTeBr angle of 176.63". The octahedron is completed through weak intermolecular bonding with a bromine atom in a neighbouring molecule at 3.591 A
and with a sulphur atom in a third molecule at 3.588 A.
The compound InTeCl has been found508to crystallize in the monoclinic
space group P2Jc, with a = 7.42, b = 14.06, c = 7.07A, and = 92.1".
The compound represents a new ternary, defect-tetrahedral, type. Strongly
distorted InTe&l tetrahedra form layer complexes situated parallel to the
(100) plane by sharing corners and edges which are occupied by tellurium
atoms. The chlorine atoms belong to one tetrahedron only and therefore do
not contribute to the linkage. The tellurium atoms are surrounded by three
indium atoms in an approximately trigonal-pyramidal arrangement.
The microwave spectra of twelve isotopic species of TeF,Cl have been
reported.609The r, distance of the Te-Cl bond was determined directly from
the rotational constants as 2.250 A. Although a unique determination of the
remaining three structural parameters was not possible, the variation of
r(Te-F)axial and r(Te-F)equaLorial,as a function of the FTeF,,,, angle, was
determined. The reactions of Me4Sn, Mq(Si,Ge,Sn)CI, and SiCl, with
HOTeF, or AgOTeF, have been shown510to give Me3(Si, Ge, Sn)OTeF, and
Si(OTeF5)4.The compound Me3SiOTeF, has been tested as a reagent for the
transfer of the F,TeO group in metathetical reactions with fluorides, and the
structures of the adducts of Me3SnOTeF, with MeCN and Me,SO have been
studied by i.r. and n.m.r. spectroscopy. The reaction of BCl, with pentafluoroorthotelluric acid at -89 "Chas been shown511to lead to the formation of the
606
608
60s
610
611
A. Bujewski and J. Dobrowloski, Roczniki Chem., 1973, 47, 401.

C. Knobler and J. D. McCullough, Znorg. Chem., 1972,11, 3026.
G. Roos, G. Eulenberger, and H. Hahn, 2.anorg. Chem., 1973, 396, 284.
A. C. Legon, J.C.S. Faraday 11, 1973, 69, 29.
F. Sladky and H. Kropshofer, J.C.S. Chem. Comm., 1973,600.
F. Sladky, H. Kropshofer, and 0. Lietzke, J.C.S. Chem. Comm., 1973, 134.
42
644
compound B(OTeF,),:
BCI,
+ 3HOTeF5
3HC1
+ B(OTeF,),
The compound melts at 37 OC and may be sublimed at room temperature in

vacua Above 14OoC decomposition to BF,, TeF,, TeO,, and a colourless,
highly viscous I iquid with the possible formulation F,Te(OTeF,),,OTeF,,
where n = 25, takes place.
The stereochemistry of oxides, fluorides, and oxide fluorides of Te4+with
AX4E polyhedra has been discussed.512The regions of glass formation in the
system Ge-Te-I have been studied.513 Hydrothermal crystallization conditions in the Sb-Te-I-R-H,O
system, where R = solvent, have been
examined.514Temperature and pressure were found to have no effect on phase
formation but EtOH was found to accelerate the crystallization process.
Compounds with a Te-S Bond.-The lattice parameters of the compound
BaTeS,,2H20 have been determined from Weissenberg and precession
photographs.515The S-S distances of the TeS, tetrahedra are 3.58 and 3.86 A
and of the adjacent TeS, groups 3.68-3.80 A. The TeS, groups form layers
parallel to the a-axis, which are separated by the Ba ions and the H 2 0
molecules. The structures of the two isomorphous compounds CI,TeS, and
Br2TeS, have been determined.516 The molecular unit (61) may be derived
x
I
from that of S8 by the substitution of one sulphur atom by the X,Te group,
Bis(N-phenylthiourea)tellurium(Ir)
dichloride and bis(NN'-diphenylthiourea)tellurium(Ir) dichloride have been isolated and their reactivity
patterns assessed.517The tellurium-sulphur bond in these complexes is weaker
than in TeII thiourea complexes. In organic complexes bis(N-pheny1thiourea)tellurium(r1) dichloride suffers dehydrochlorination to yield a glassy Te'I
imido-chloro-complex.
The complex trans-dimethanethiosulphona t obis (ethylenet hiourea)tellurium(zI), Te(etu),(S,O,Me,),, crystallizes in two forms: a triclinic form (I), of
space group Pi, with a = 9.519, b = 10.210, c = 5.385L$, OL = 98.88',
518
613
S. Anderson, A. Astrom, J. Galy, and G. Meunier, J. Solid-state Chem., 1973,6 , 187.

A. Feltz and H . 4 . Buttner, Z . Chem., 1972, 12, 392.
514
V. I. Popolitov and A. N. Lobachev, Izvest. Akad. Nauk. S.S.S.R., Neorg. Materialy,
515
516
517
1973,9,210.
H. Gertl and H. Schaefer, 2. Nuturforsch., 1972, 27b, 1421.
J. Weiss and M. Pupp, Acta Cryst., 1972, B28, 3653.
P. R.Setheraman, M. R. Udupa, and G. Aravamudan, Indian J . Chem., 1973,11,288.
Elements of Group V l
645
= 105.54', and 7 = 98.89'; and a monoclinic form (IT), space group

P2,/c, with a = 9.616, b = 10.850, c = 10.672 A, and = 119.21O. The
crystal and molecular structures of both forms have been determined51sby
three-dimensional X-ray methods. The centrosymmetric square-planar
TeS, co-ordination groups (Figure 11) are very similar in the two dimorphs :
Te-S (etu) = 2.663 A in I and 2.687 A in 11; Te-S (thiosulphonate) =
2.694 A in I and 2.685 A in 11; the bond angles STeS = 91.6' in I and 92.6'
in 11; LTeSS = 103.9' in I and 102.3' in 11.
Figure 11 trans-Dimethanethiosulphonatobis(ethylenethiourea)tellurium(rI),as
seen normal to the TeS, co-ordinationgroup. Left: triclinic dimorph;
right: monoclinic dimorph. Telluriumatoms in centres of symmetry
(Reproduced by permission from Acta Chern. Scand., 1973, 27,218)
The crystal structure of tetrakis-(4-morpholinocarbodithioato)tellurium(1v)

has been deterrni11ed.5~~
The Te atom is found to be eight-co-ordinated by
sulphur atoms (62) in a dodecahedra1 D,, arrangement. The dodecahedral TeS, group has a structure similar to that found520for the corresponding group in tetrakis(diethyldithiocarbamato)tellurium(Iv) and thus
the lone pair of electrons in the valency shell of the central Te atom is essentially stereochemically inert. Te(Et,NCS,)4 forms flat, prismatic, orange
crystals belonging to the orthorhombic space group Pn2,a. The asymmetric
51s
5a0
0. FOSS,
N. Lyssandtrae, K. Maartmann-Moe, and M. Tysseland, Acta Chern. Scand.,
1973, 27, 218.
S. Esperas and S. Husebye, Acta Clicm. Scand., 1973, 27, 706.
S. Husebye and S. E. Svaeren, Acta Chem. Scand., 1973, 27, 763.
646
unit comprises two crystallographically independent but very similar molecules. The central tellurium atom is bonded to all eight sulphur atoms in each
molecule in a slightly distorted dodecahedra1configuration, with Te-S bond
lengths varying between 2.631 and 2.845 A and an average bond length of
2.744A. For comparison, the eight Te-S bond lengths in tetrakis-(4morpholinocarbodithioato)tellurium(Iv) range between 2.672 and 2.824 A,
with an average of 2.74 A. The dodecahedron in Te(Et,NCS2)4can be visualized as being made up of two interleaving, planar, trapezoids at right angles
to each other. One such trapezoid is shown in (63).
The crystal structure of barium telluropentathionate trihydrate BaTe(S,O&,3H20 has been determined.521The salt crystallizes in the monoclinic space
groupP2,/c, with theunit-celldimensionsa = 11.139,b = 5.243,~=21.306&
and = 106.94". The telluropentathionate ion has the trans-configuration
(64), the sulphonate groups being rotated out of the plane of the three middle
atoms to different sides of the plane. The dimensions of the S-S-Te-S-S
chain from one end of the chain to the other are S-S = 2.102 A, S-Te =
2.384 A, Te-S = 2.392 A, S-S = 2.090 A, LSSTe = 103.08', LSTeS =
96.02', and LTeSS = 102.59'.
The telluropentathionate ion adopts the cis-form in the monoclinic dimorph
of the trihydrate of barium telluropentathionate BaTe(S20,),,3H,0. A
crystal-structure deterrninati~n~~,
has shown that mirror-plane symmetry is
62a
sal
K. Gjerrestad and K. Marsy, Acta Chem. Scand., 1973, 27, 1653.

K. Marpy, Acta Chem. Scand., 1973, 27, 1695.
EIements of Group VI
647
crystallographically required for the telluropentathionate ion, and the ion

thus occurs in the cis-form (65). The dimensions of the S-S-Te-S-S
chain in this form are S-S = 2.104 A, S-Te = 2.377 A, LSSTe = 103.79',
and LSTeS = 100.29O.
The Ge-Te-S ternary system has been established;523GeTe-GeS, and TeGeS, were found to be quasi-binary sections, with the ternary eutectic compositions of GeGeTeGeS, and GeTeTeGeS, being approximately fixed
and the quasiperitectic liquid composition (Liquid Ge 7GeTe GeS)
precisely fixed.
Interaction of TeIV with excess thioglycollic acid in strongly acid media
leads to the formation of yellow, diamagnetic, soluble, S-ligated thioglycollatotellurium(I1) neutral and anionic complexes.524The neutral bis-complex
is highly unstable with respect to autodecomposition to Teo and dithioglycollic
acid but the anionic higher complexes are stable in the absence of competing
ligands.
623
624
S. Maneglier-Lacordaire, J. Rivet, P. Khodadad, and J. Flahaut, Bull. SOC.chim.

France, 1973, 1930.
G. Avaramudan, P. R. Sethuraman, and M. R. Udupa, J . Inorg. Nuclear Chem., 1973,
35, 3291.

648
Tellurides.-A brief review (8 references) has been
of the chalcogenides of both non-metals and semi-metals. The equilibrium phase diagram
of the Li-Te system has been investigated.526Eutectic points were observed
at 179.9 OC (99.0 atom% Li), 448.5 O C (35.7 atom% Li), and 423.1 "C
(10.5 atom% Li); two intermediate phases, Li,Te and LiTe,, were present,
having melting points of 1204.5 and 459.9 "C,respectively. A heterogeneous
equilibrium
of the Te-Ba and Te-Sr systems has revealed that the
compounds BaTe and SrTe may be formed, since both systems exhibit a
eutectic and limited solubility. The formation of the tellurides InTe, GaTe,
In2Te3, and Ga,Te, from the elements has been
to take place in
stages. At relatively low temperatures the compounds In,Te and Ga,Te are
formed, with the normal tellurides forming at higher temperatures. The
specific heats of GaTe and InTe have been measured.529The following new
ternary tellurides have been prepared530by solid-state reactions of the
elements at 1050 "C in argon; SrA1,Te4, SrGa,Te,, SrIn,Te4, BaAl,Te,,
BaGa,Te,, BaIn,Te,, BaA1,Tel,, NaInTe,, and KInTe,. All the compounds
crystallized in the tetragonal space group 14/mcrn,with lattice constants in the
ranges a = 8.21-8.52, c = 6.72-7.39 A except for Ba,A1,Te16, which had
a = 34.24 and c = 6.70 A. Single-crystal studies have confirmed531that the
compounds TlGaTe,, TlInSe,, and TlInTe, crystallize in the TlSe type of
structure. Thallium is surrounded by eight chalcogen atoms, whilst gallium
and indium have tetrahedral co-ordination and covalent bonds.
of the alloy Gel~,,Te,,,,5 in the amorphous
A neutron-scattering
and liquid states has shown that a change in co-ordination number from 2.43
to 3.25 takes place on melting. In the liquid state the observed co-ordination
number can be fitted by assuming four-fold co-ordination of Ge and threefold co-ordination of Te, whilst in the amorphous state four-fold co-ordination
of Ge and two-fold co-ordination of Te is assumed. The dependence of the
structure of thin films of (SnTe)l,,(PbSe), and (SnTe),,(PbTe),
on the
phase composition (0 Q x 6 1) and on the conditions of preparation has
been reported?,, Thermochemical data have been obtained5= for alloys of
tellurium with tin and lead over the whole range of concentrations.
525
626
G . V. Samsonov, Khal'Kogenidy, 1970, 2, 22.

P. T. Cunningham, S. A. Johnson, and E. J. Cairns, J. Electrochem. SOC.,1973, 120,
328.
647
Yu. B. Lyskova and A. V. Vakhobov, Doklady Akad. Nauk. Tadzh. S.S.R., 1973,16,
35.
6.28
629
630
631
634
633
M. Yu. Abdullaev, Noo. Poluprov. Muter., 1972, 104.

K. K. Mamedov, I. G . Kerimov, M. I. Mekhtiev, and E. A. Masimov. Izoest. Akad.
Nauk. S.S.S.R., Neorg. Materialy, 1972, 8 , 2096.
E. R. Franke and H. Schaefer, Z . Naturforsch., 1972, 27b, 1308.
D. Muller, G. Eulenberger, and H. Hahn, 2.anorg. Chem., 1973, 398, 207.
E. Nicotera, M. Corchia, G. DeGiorgi, F. Villa, and M. Antonini, J. Non-cryst.
Solids, 1973, 11,417.
D. M. Freik, V. V. Voitkiv, G. M. Gaiduchok, and I. 1. Brodin, Soviet Phys. Cryst.,
1973, 17, 964.
634
R. Castanet, Y . Claire, and M. Laffitte, High Temp.-High Press., 1972, 4, 343.
649
Phase relationships in the following systems have been studied: G e T e and
Pb-Te,535As-Ge-Si-Te and GeSi-Te,536CdTe-Sn,637and PbTe-MgTeF3*
The arsenic-tellurium phase diagram has been re-examined;539two eutectic
points were found but no miscibility gap. The influence of the composition on
both the viscosity and interfacial tension in the liquid state was analysed from
supercooling measurements. Amorphous As2Te, films have been studiedsg0by
electron diffraction; the structure of the films apparently consists of trigonal
pyramids joined together such that the octahedral arrangement of tellurium
atoms near the arsenic atoms which is present in the crystalline form is absent
in the amorphous form. 125TeMossbauer spectra of Seo.98Teo.02
alloys in bulk,
amorphous, and trigonal phases have been studied.541The chemical stability
of the tellurides of the vanadium group of transition elements has been
The tellurides are hardly affected by H 2 0 but are completely decomposed by oxidizing acids :
V2Te, + HCl -+H2Te
+ VCl,
Decomposition by alkalis takes place with the formation of elemental

tellurium.
5 Polonium
The separation of 210Poand 210Bifrom 210Pbmay be accomplished by drying

on to a platinum surface followed by selective desorption with appropriate
solvents.543A new isomer with a half-life of 58 f 2 ms has been observed544
in 2 0 s Pby
~ the reactions 207Pb(a,6n)205Po
and 204Pb(a,3n)205Po,
with 69 MeV
and 38 MeV a-particles, respectively. The 210Poactivity of the lunar surface
is significantly higher than the activity of its progenitor 222Rnaccording to
measurements made with the Apollo 16 or0 spectrometer.545There are large
variations and well-localized enhancements in 210Poactivity over much of the
lunar surface.
A. D. Bigvava, E. D. Kunchuliya, S. S. Moiseendo, E. P. Sabo, and P. Shvangiradze,
Zzvest. Akad. Nauk. S.S.S.R., Neorg. Materialy, 1972, 8, 2089.
A. Feltz, W. Maul, and I. Schonfeld, Z . anorg. Chem., 1973, 396, 103.
5 3 1 0. E. Panchuk, L. P. Shcherbak, I. E. Panchuk, and I. N. Antipov, Zzoest. Akud. Nuuk.
6 3 8 A. J. Crocker and B. J. Sealy, J . Phys. Chem., Solids., 1972, 33,2183.
539 J. Cornet and D. Rossier, Muter. Res. Bull., 1973, 8, 9.
5 4 0 Yu. G. Poltavtsev, V. P. Zakharov, and V. I. Shvets, Ukrain.fiz. Zhur., 1973,18,663.
5 4 1 P. Boolchand, Solid State Comm., 1973, 12, 753.
5 4 2 V. A. Obolonchik, L. S. Vainer, and A. A. Yanaki, Russ. J. Inorg. Chem., 1972, 17,
1220.
543 H. N. Kirby, J. Inorg. Nuclear Chem., 1973, 35, 2043.
644
B. Focke, A. Goldman, J. Hadizuana, M. Von-Hartropp, K. Nishiyama, and D.
Riegel, Z. Physik, 1973, 259, 269.
545
P. Bjorkholm, L. Golub, and P. Gorenstein, Science, 1973, 180, 957.
635
536
The Halogens and Hydrogen

BY M. F. A. DOVE
1 Halogens
Elements.-A gas-flow 122Tepowder target for the cyclotron production of

B+
pure 1231has been described? The reaction involved is 122Te(4He,3n)123Xe
4
1231.Yields in the range 2 4 mCi h-l have been obtained from 1.5 g 122Te.
The la41contamination could be held as low as 0.001 %, whereas the 1251
contamination was 0.4 %.
The refractive index, n, of gaseous fluorine at room temperature has been
measured at a number of wavelengths and for medium pressures;2the results
were fitted to the equation n - 1 = 20.87 x
(1
6.4 x
F2),
where A is the wavelength of light in microns. Measurements of the velocity of
sound in liquid fluorine have been reported for the first time? Data were obtained at 110 and 130 K at pressures up to 21 MN mV2and should be accurate
to within a few percent. Intensity decay of fluorine (F I1 to F VII) emission
lines, between 380 and 1200 A, has been measured*and shown to be in good
agreement with recent theories.
The Raman spectra of gaseous, liquid, and solid chlorine have been
reinvestigated.6 In addition to the fundamentals corresponding to various
isotopic species, hot bands have also been assigned, and the temperature
dependence of their intensities has been measured in the range 150-350 K.
Vibrational structure has been resolved in the first two bands in the N e I
photoelectron spectrum of iodine.6 The adiabatic ionization potential was
established by temperature-variation studies, and the spectroscopic ionization potentials for both bands were found to correspond to the production
of ions with three vibrational quanta.
Evidence for the production of the doubly charged negative fluorine ion
Fa- has been described by Ahnell and Koski;' the new species was obtained
from the electron bombardment of CF3CI (but not from CFd.
V. J. Sodd, J. W.Blue, K. L. Scholz, and M. C. Oselka, Internat. J . Applied Radiation

Isotopes, 1973, 24, 171.
a W. F. Rumpel, G. Yanow, and D. F . Penning, J. Chern. Phys., 1972,57,3011.
G. C. Straty and B. A. Younglove, J. Chern. Phys., 1973,58,2191.
L. Barrette and R. Drouin, Canad. J . Spectroscopy, 1973, 18, 50.
F.Wallart, Cartad. J. Spectroscopy, 1972, 17, 128.
B. R. Higginson, D. R. Lloyd, and P. J. Roberts, Chem. P h p . Letters, 1973, 19,480.
J. E. Ahnell and W. S. Koski, Nature Phys. Sci., 1973,245, 30.
650

651
In describing a new method (involving U.V. photolysis) for the synthesis of
NF,AsF,, Christe, Wilson, and Axworthys have postulated that the initial
photolytic production of fluorine atoms is followed by the generation of
AsF,. radical. This is thought to be the reactive intermediate in both thephotolytic and thermal fluorination reactions and, according to their results,
AsF,. is comparable in reactivity with PtF, as an electron-abstracting agent.
The behaviour of the product vibrational distributions in the reaction
F (HID),-+ (HID)F (HID) has been studied, using chemical laser
methods: as a function of reactant temperature. This study provides the
first quantitative evidence that the distributions are temperature-dependent.
The kinetics and mechanisms of the reactions of atomic fluorine with CF,I
and CC1,Br have been investigated in a fast-flow reactor using molecular
beam analysis.1 The direct observation of perhalogenomethyl radicals and
the apparent absence of displaced halogen atoms has shown that both
reactions proceed primarily by abstraction, rather than displacement, of a
halogen atom. The relative rates of hydrogen atom abstraction by 18Fatoms
have been measured for H,, CH,, C,H,, CH,CF,, H2S, and HI uersus the
rate of addition to acety1ene.ll Sulphur hexafluoride was used as a moderator
in these reactions as well as a source of 18F,via the 19F(n,2n)18F reaction. In
another study of relative rates the known chemiluminescent reaction F +
NO + Ar +. FNO* Ar --f FNO Ar + hv was followed photometrically to monitor the disappearance of fluorine atoms. In this instance the
reactions studied were those with CH,, CH,F, CH,F,, CHF,, CHClF,, HCl,
CBrF,, NH,, and PH,.12
The electrochemical behaviour of the couple HglHg,F2 in anhydrous HF
has been investigated by Mougin and Royon and has been found suitable for
use as a reference electrode in this medium.13 Measurements of the potentials
of the couples PtlH,(HF) and NilF,(HF) gave -0.58 and +2.25 V, respectively, at25'C; these values are consistent with accepted values for the solvent
oxidation and reduction processes. Tetrafluoroborate salts have been shown
to participate in electrolyses in certain aprotic media, and substantial yields
of products of anodic fluorination have been obtained.14 Thus the conversion
of benzhydryl p-toluyl ketone to p-toluyl fluoride (65 %) was achieved.
The electrode reaction 1, + 2e--+ 31- is extremely fast, the exchange
currents being of the order of 0.3 A cm-, on platinum and graphite.15 On
account of the possible use of this reaction at the cathode in an iodine-metal
K. 0. Christe, R. D. Wilson, and A. E. Axworthy, Inorg. Chem., 1973, 12, 2478.

R. D. Coombe and G. C. Pimentel, J. Chem. Phys., 1973,59,251.
l o J. W. Bozzelli and M. Kaufman, J. Phys. Chem., 1973,77, 1748.
l1 R . L. Williams and F. S. Rowland, J. Phys. Chem., 1973,77, 301.
l2 T. L. Pollock and W. E. Jones, Canad. J . Chem., 1973,51,2041.
l3 J. Mougin and J. Royon, Compt. rend., 1973, 276, C,819.
l4 V. R. Koch, L. L. Miller, D. B. Clark, M. Fleischmann, T. Joslin, and D. Pletcher,
J . Electroanalyt. Chem. Interfacial Electrochem., 1973, 43, 318.
l6 H. S. Wroblowa and A. Saunders, J. Electroanalyt. Chem. Interfacial Electrochem.,
1973,42,329.

652
or -hydrogen fuel cell, a study has been made of an Is[I- graphite flowthrough electrode in order to establish the optimum electrode performance.
Estimates of the thermochemical parameters AH: and Sofor Xiq and XGaq),
for X = Br or I, have been reported by Woodruff and Margerum,16and oneelectron electrode potential data were deduced from these estimates. The
Ea/V data arrived at in this way are as follows:
1.087
0.6197
Methyl iodide has been identified by g.c. as the sole gaseous product arising
from the photolysis of CH,-12 mixtures at 147 nm.17 Measurements of the
CHJ quantum yield suggest that
atoms are important intermediates
in this system. Sub-microsecond transient absorptions in the 250-400 nm
spectral range produced by laser (529nm) flash photolysis of I,, in H,O,
MeOH, and Pr'OH, have now been attributedl8 to charge-transfer complexes
of iodine atoms with the solvent molecules. The 385 nm transient absorption
previously assigned to these species is now thought to be due to I;. On the
other hand, the reactions of iodine, excited with 185 nm radiation, with H,,
O,, hydrocarbons, and halogenocarbons proceed via excited iodine molecules
and not via iodine atoms.lg The reaction O(3P) B r 2 e X 3 + Br0(211)
Br(2P) takes place via the formation of a persistent collision complex, with
a large reaction yield and no activation energy.2O An unsymmetric 0-Br-Br
complex is favoured rather than the known, stable Br,O molecule. The
oxygen-atom reactions with Cl,, I,, ICl, and IBr appear to be quite analogous.
The laser Raman spectrum of F; has been obtained for the first time.21
Reaction between F, and alkali metals in an argon matrix at 15 K gave rise to
the product, which was characterized by a Raman band near 460 crn-l. This
feature exhibited instability, due to laser photolysis, at a greater rate than that
due to F, itself (at 892 cm-l). The Raman spectra of the orange products of
the reactions between C1, and the alkali metals in argon matrices contained22
bands in the range 225-264cm-l.
First and higher overtones, showing
chlorine isotope splittings, were evident (Figure 1) using exciting lines at
4880 and 5145 A, owing probably to the resonance Raman effect. These lines
were, therefore, all attributed to Cl;. This is in agreement with the earlier
Raman study by Hass and Griscom of y-irradiated alkali-metal halide glasses.
l7
l9
2o
21
23
W. H. Woodruff and D. W. Margerum, Znorg. Chem., 1973,12, 962.

P. John, G. J. Kennedy, and B. G. Gowenlock, J.C.S. Chem. Comm., 1973, 683.
P. Fornier de Violet, R . Bonneau, and J. Joussot-Dubien, Chern. Phys. Letters, 1973,
19, 25 1 .
L. C. Glasgow and J. E. Willard, J. Phys. Chem., 1973, 77, 1585.
D. D. Parrish and D. R. Herschbach, J. Amer. Chem. SOC.,1973, 95, 6133.
W. F. Howard and L. Andrews, J. Amer. Chem. SOC.,1973,95, 3045.
W. F. Howard and L. Andrews, J. Amer. Chem. Soc., 1973, 95, 2056.
1.
1
XYJ
g
J
f2
cc,
nz
1
2100
I
1700
i
1-XCJ
3c3
1~30
FREQUERCY SHiFT
Figure 1 Resonance Raman spectrum of the products of chlorine molecule-lithium atom matrix reactions,
Ar/Cl, = 100. Instrumental parameters: exciting line approximately 50 mW of 5145 A; range (a)
1 x
A, (b) 0.3 x
A, (c) 0.1 x
A; j l t e r , 5 A dielectric spike; rise time (a) 1 s, (b) 3 s,
(c) 10 s ; scan speed, 10 cm-l min-l
(Reproduced by permission from J. Amer. Chem. Soc., 1973,95,2056)
Inorganic Chemistry of the Main group Elements
654
The theoretical maximum temperature of the H2S-F, flame has been

calculated as 3469 K:23 this was confirmed by measuring the rotational
temperatures of the 1-0 and 3-0 bands of HF. The interaction of fluorine and
graphite powder has been studied in the temperature range -78 to +200 "C
at pressures up to 160 mmHg. Watanabe and c o - w ~ r k e rdemonstrated
s~~
that
the reaction is irreversible; however, they found that the reaction product
would oxidize aqueous KI solution. A room-temperature solid-state direct
fluorination reaction has been reported to yield 85% conversions of mcarbaborane, m-BloHloC2H2,after a reaction time of 10 days.25Evidence was
also presented to show that decafluoro-m-carbaborane, rn-C,H,BloF,o, was
an intermediate in the reaction. Kennedy and Cady26have described their
systematic investigation of the influence of metal fluorides on the outcome
of the two main reactions between fluorine and carbonyl fluoride:
F2
and
F2
+ F2CO -+
+ 2FZCO
-j
FSCOF
FSCOOCFS
Whereas a wide range of fluorides are known to catalyse the former process,
rather fewer catalysts (e.g. TlF, and a mixture of AgF and AgF,) have been
found to catalyse the latter reaction: Kennedy and Cady discussed possible
mechanisms for these reactions.
Chlorine and bromine molecules were found to suppress the isotopic
H-D exchange process of D, in 1 :1 HF-SbF, solution.27Under comparable
conditions the suppressions produced by CI,, Br,, CO,, and Xe were respectively 94, 94, 33, and 30%. Olah and Shen interpreted these experiments on
the basis of the degree of protonation as well as of their solubility in the
'super-acid' medium. The chlorine-water system has been reinvestigated by
Wilms and van Haute;,* they determined the composition of chlorine hydrate
in three independent ways. The variation of the composition of C12,nH,0
with temperature was found to range from n = 7.05 at -0.22 OC to 6.61 at
+9.28 'C. The i.r. spectrum of 1 :1 H20-CI, complex in a nitrogen matrix at
20 K has been recorded.29 A hydrogen-bonded interaction was thought
improbable since only slight changes in the vibrations due to H 2 0 occurred
on complex formation. Instead it was assumed that the geometry of the
complex was C,,,with 0. Cl-CI collinear. On the basis of isotope substitution studies, LHOH in the complex was estimated to have increased by
about 1.5".
23
24
26
26
27
2g
J. Chevaleyre, C. Matray, and J. Janin, Spectrochim. Acfa, 1973, 29A, 1091.

R. J. Lagow and J. L. Margrave, J. Znorg. Nuclear Chem., 1973,35,2084.
R. C. Kennedy and G . H. Cady, J . Fluorine Chem., 1973, 3,41.
G. A. Olah and J. Shen, J. Amer. Chem. SOC.,1973, 95, 3582.
D. A. Wilms and A. A. van Haute, Desalination, 1973, 12, 379.
L. Fredin and B. Nelander, J. Mol. Structure, 1973, 16, 217.

655
The kinetics of the photochemical reaction of chlorine and trifluoroacetaldehyde have been investigated.3O The reaction proceeds nearly quantitatively at
room temperature according to the equation:
CF,CHO
+ CI, + hv
--.t
CF,COCI
+ HCl
The reaction is thus quite unlike those between chloral and either C1, or Br,,
in which C-C bond cleavage is dominant. However, at higher temperatures
the yield of CF3COC1 is diminished and CF,Cl is formed along with CO. A
mechanism for the uncatalysed reaction:
HzOa
+ CIS + 2HC1 + Oz
in aqueous solution has been put forward by Davies and Kustin31 which is
consistent with the best available evidence concerning the nature of the
reaction intermediates. Since numerous attempts to furnish more conclusive
evidence for the existence of HOOCl have failed, the proposed mechanism is
based on the production of H,Ol and Cl;, in the simple electron-transfer
reaction :
H20t
+ C12 -+
H,O$
+ C1;
An ethylene-chlorine complex (probable stoicheiometry 1:1) has been prepared in a nitrogen matrix at 20 K and characterized by U.V. and i.r. spectrocopy.^^ The i.r. data are consistent with C,, symmetry but do not throw any
light on the prediction that the CI-Cl bond is orthogonal to the plane of the
C,H4 molecule.
Energy parameters and charge-transfer spectra of complexes of Br, with
several substituted pyridines have now been compared with the force constants
k(Br-Br) and k(N. * -Br2)and with the properties of the donors.33The complexes with ortho-substituted pyridines show systematic deviations from the
relations found to be valid for the other donors. The lH n.m.r. spectrum of the
pyridine-Br, complex in a nematic phase has been obtained and a n a l y ~ e d . ~ ~
The results indicate that the donor-acceptor interaction is similar to that
found in the solid state for other halogen-pyridine complexes. The equilibrium constant for the formation of the 1 :1 complex of Br, with hexamethylphosphortriamide (HMPA) has been determined by lH n.m.r. spectrocopy.^^ Solid adducts of Br, with poly-HMPA could also be prepared.
The charge-transfer complexes formed by iodine with ethane- and benzenethiols, diphenyl sulphide, and diphenyl disulphide have been investigated in
cyclohexane at 25 OCF6 Spectroscopic data for the 1 :1 complexes and the
so
L. Antonelli, E. Castellano, and H. J. Schumacher, 2.phys. Chern. (Frankfurt), 1973,
31
G. Davies and K. Kustin, Inorg. Chern., 1973, 12, 960.

L. Fredin and B. Nelander, J. Mol. Structure, 1973, 16,205.
P. Hyskens, J. D'Hondt, F. Govaerts, and Th. Zeegers-Huyskens, J . Phys. Chem.,
84, 188.
32
33
1973,77, 1662.
34
36
36
C. A. Veracini, M. Longeri, and P. L. Barili, Chem. Phys. Letters, 1973, 19,592.

Y.Ozari and J. Jagur-Grodzinski, J.C.S. Dalton, 1973,474.
G. Reichenbach, S. Santini, and U. Mazzucato,J.C.S. Faraday I , 1973,69, 143.
656
thermodynamics of complexation were reported. The stability constants for

the complexes formed by para- and rneta-substituted thiophenols are linearly
related to the Hammett c constants for the substituents, thus supporting the
view that these complexes are of the n-o* type. Novel adducts of iodine with
N-iodomethylamines, [MeNI,],I,, [Me2NI],I,, and Me,NI,I,, have been prepared and their i.r. spectra interpreted on the basis of molecular adducts
between the nitrogen bases and
A labile 1:1 complex of I2 with Si(OEt),
has been investigated in CCI, solution and its stability constant e ~ t i m a t e d . ~ ~
When iodine dissolves in pure s-butylamine it is quantitatively reduced to
iodide, the oxidation product being sym-di-s-b~tylhydrazine.~~
On the other
hand, t-butylamine is oxidized much more slowly, so that the bright orange
amine-I, (1 :1) adduct can be isolated. The specific conductances of solutions
of iodine in acetoneto dimethyl sulphoxide,4 and 1,1,3,3-tetramethyl~rea~~
have been measured and found to be time-dependent. In acetone solutions
(ca.
mol l-l, 1 0 4 5 "C) the conductances rose to a maximum and then
diminished; in dimethyl sulphoxide the values increased uniformly with time.4O
Halides.-An X-ray electron study of the fluorine 1s line in the series BeF,
NaBeF,-Na,BeF, and ZrF4-KZrF5,H20-K,ZrF6-K3ZrF7 has shown42that
there is a systematic decrease in the binding energy with increasing fluorine:
metal (Be or Zr) ratio. On the other hand, no such trend was observed for the
series TaF;-TaFi--TaF:-.
The F 1s lines for Cs,Mo(W)O,F, and K,NbOF5
were found to be broadened; this was attributed to the non-equivalence of the
fluorine atoms in these compounds. Bhat43has reported the X-ray K absorption spectra of chlorine in a number of complex compounds. An interesting
correlation was apparent between the intensity of the narrow selective absorption line appearing on the low-energy side of the edge and the degree of
covalency of the metal-chlorine bond.
Ion-cyclotron resonance spectroscopy has now been used to investigate
chloride ion clusters, e.g. CI-(CH3N02), in the gas phase at pressures between
5 x
and 4 x 10-4Torr?4 Relative clustering (solvating) abilities were
assessed, e.g. EtCl < MeNOz w MeCN M MeOH; the trends obtained were
found to be compatible with those established by high-pressure mass spectroscopy. Halide-ion solvation in the polar solvents H20, MeOH, MeCN,
DMSO, and DMF has been studied by 35C1,79Br,and 12'1 n.m.r. spectrosc0py.4~A close correlation between the chemical shifts and the chargetransfer-to-solvent U.V. absorption band energies strongly suggests that the
W. Knuth, W. Renz, and J. Jander, Z . anorg. Chem., 1973, 400, 67.
A. Ya. Deich, Zhur. obshchei Khim., 1973, 43, 1080.
39 J. C. Schug and M. J. Kogan, J . Magn. Resonance, 1973, 11,406.
O0 T. E. Hanson and B. Musulin, Znternat. J; Sulfur Chem., 1972,2, 125.
*l B. J. Barker and J. A. Caruso, Electrochim. Acta, 1973, 18, 315.
42 V. I. Nefedov, Yu. V. Kokunov, Yu. A. Buslaev, M. A. Porai-Koshits, M. P. Gustyakova, and E. G. Il'in, Russ. J. Inorg. Chem., 1973, 18, 490.
O3 N. V. Bhat, Spectrochim. Acta, 1973, 28B, 257.
O4 J. M. Riveros, A. C. Breda, and L. K. Blair, J . Amer. Chem. SOC.,1973, 95,4066.
OG T. R. Stengle, Y.-C. E. Pan, and C. H. Langford, J. Amer. Chem. SOC.,1972,94,9037.
38

657
paramagnetic term is dominant in determining n.m.r. shifts and that the important excited state is the CTTS state.
The heteroconjugates of pyrocatechol with X-- (X = C1, Br, or I) and
Cloy; ions in nitromethane solution have been studied by lH n.m.r. spectroscopy.46 The formation constants of the 1:l complexes are 418, C1-; 187,
Br-; 27.8, I-; 11.2 1mol-l, ClO,. The pyrocatechol-anion interaction is
believed to be due to two (chelate type) hydrogen bonds to the anion. The
complex with Cloy would then be the first quantitative evidence for hydrogenbonding to this ion. 12-Molybdosilicate and 12-molybdophosphate anions
were found to be less susceptible to this kind of interaction with pyrocatechol.
The nucleophilic reactivity of F- for substitution at MeCl has been determined
quantitatively in the gas phase using the flowing afterglow technique:
F-
+ MeCl
---+
MeF
+ C1-
comparisons were made with gas-phase basicities and nucleophilic reactivities

in solution.47
Traces of fluoride can be extracted from aqueous solution with Et,SiCl in
m-xylene or with Ph,SbOH in CH2C12and can be coprecipitated by adsorption
on hydroxyapatite.**A gas-chromatographic method was also investigated
in which sub-microgram quantities of fluoride were determined as Et,SiF.
The use of lithium tetraborate has been proposed49as an alternativereagent for
decomposing fluorine-containing materials. Thus whereas alkaline fusion at
950 OC can lead to losses of F,with this lithium salt no losses were reported
after 5 minutes reaction at 1200C. Selig50 has described how the known
addition method can be used in combination with Grans plots and a
fluoride-ion-selective electrode for the determination of 0.08 to 3 p.p.m.
fluoride. The effectiveness of three different total-ionic-strength adjustment
buffers was also investigated. A minor modification has been described51
which permits a more accurate gravimetric determination of F- as Ph,SnF.
Kolthoff and Yutzis method has been compared52with Denoels for the
determination of C1 and Br in geochemical samples; the former has been
found to give the more consistent results over a wider range of the C1:Br
ratio, A colorimetric determination of iodine in the form of nitron triiodide has been shown to be effective with solutions containing 2 to 20 pg of
iodine per 25 ml, even in the presence of C1- and Br-.53
Interhalogens and Related Compounds,-Meinert and Gross53have reviewed
the chemistry of the halogen fluorides with particular emphasis on the selfionization phenomena. The inorganic chemistry of the halogen cyanides has
46
47
48
4s
6o
51
52
6s
L. Barcza and M. T. Pope, J. Phys. Chem., 1973,77, 1795.

L. B. Young, E. Lee-Ruff, and D. K. Bohme, J.C.S. Chem. Comm., 1973, 35.
R. Bock and S. Strecker, Z . analyt. Chem., 1973,266, 110.
W. Rechenberg, Z . analyt. Chem., 1973,263, 333.
W. Selig, Mikrochim. Acta, 1973, 87.
J. Tscholakowa, Z . analyt. Chem., 1973,266,288.
M. Chaigneau and M. Chastagnier, Bull. SOC.chim. France, 1973, 944.
H. Meinert and U.Gross, J. Fluorine Chem., 1973, 2 , 381.
658
also been reviewed (up to May 1972) by Ma~Cordick,~*

whereas Dehni~ke,~
has reported on the halogenation reactions of the following halogen(1)
compounds: ClF, C1,0, ClNO,, BrC(CN),.
The temperature dependence of the CIFaq)n.m.r. linewidth in the presence
of C1, has been studied from -50 to +30C.56a The C1- ion dependence
indicated that chemical exchange could be associated with the equilibrium
CICl, + Clg. Because these and other results from this work are in
qualitative disagreement with those of Hall et al.,56b further independent
studies are evidently needed. Ab initio calculations have shown that ClF, can
be regarded as being derived from CIF with the addition of two fluorine atoms
by way of a three-centre bond.,' The involvement of 3d orbitals on C1 in this
ClF, bonding was discussed. Shaw et aL5*have demonstrated that ESCA can
be used to distinguish between fluorine atoms that differ only in their geometric orientation with respect to the same central atom. The 1s binding
energiesfor the axial and equatorial fluorines in CIF, were measured and found
to be 692.22(3) and 694.76(4) eV, respectively: the assignments were made on
the basis of the relative intensities. The lower binding energies of comparable
electrons in the axial sites (of CIF,, PF,, and probably SF,) are consistent with
the view that these fluorines are bonded to the central atom with partially
ionic, three-centre bonds.
The addition of a Lewis acid to ClF forms Cl,F+ and enhances the oxidizing
power of CIF to such an extent that it can fluorinate Xe according to:59
Cl,F+AsF;
+ Xe
XeF+AsF;
followed by:
2XeF+AsF,
Xe,FgAsF,-
+ CI,,
+ AsF,
A more complete account of the synthesis of C I q P t q has appeared.6O The

displacement reaction with FNO at -78 "Cdid not yield CIF,, but took place
according to :
CIFtPtF;
+ FNO + NO+PtF; + ClF5 + Fz
Unsuccessful attempts were made to prepare CIF&B& by low-temperature

discharge of a ClF,-F,-BF, mixture and to prepare other ClFt salts by the
high-temperature/high-pressure reactions of CIF5-F,-SbF,(AsF,, BF,).
Christe, Hon, and PilipovichG1have carried out a lgF n.m.r. study of
chlorine fluoride and oxide fluoride cations in anhydrous HF. Their results
57
J. MacCordick, Bull. Soc. chim. France, 1973, 55.

K. Dehnicke, Chimia (Switz.), 1973, 27, 309.
(a) H. W. Dogden, A. D. Jordan, and R. B. Jordan, J. Phys. Chem., 1973,77, 2149;
( 6 ) C. Hall, D. W. Kydon, R. E. Richards, and R. R. Sharp, Proc. Roy. SOC.,1970,
A318, 119.
A. Breeze, D. W. J. Cruickshank, and D. R. Armstrong, J.C.S. Faraday ZZ, 1972, 6 8 ,
68
R. W. Shaw, T. X. Carroll, and T. D. Thomas, J. Amer. Chem. SOC.,1973, 95, 2033,
54
66
66
2144.
5870.
58
8o
K. 0. Christe and R. D. Wilson, Znorg. Nuclear Chem. Letters, 1973, 9 , 845.

K. 0. Christe, Znorg. Chem., 1973, 12, 1580.
K. 0. Christe, J. F. Hon, and D. Pilipovich, Znorg. Chem., 1973, 12, 84.

659
and those of earlier workers are summarized in Table 1.62-66 In several
instances it was found necessary to acidify the solution of the complexes by
the addition of a fluoride acceptor in order to produce a separate cation resonance; thus before acidification of solutions containing ClFa or F,ClOf salts
the cation resonance appeared to have merged with that of the solvent.
Mills and Schneider6' have discussed the use of BrCl as an alternative to
Br, for industrial bromination work. The Raman spectrum of liquid BrCl has
Table 1 Summary of the I9F n.m.r. spectra of chlorine fluorides and oxide
fluorides and their derivatives
Compound
ClF
CIFZF
ClF,F_)
ClF;
Temp.l"C
-80
C
ClE,F
1F4E
CIFZt
CIGF:)
CiF;
FClO,
FC103
F3CI0
F&IO+
F3C102
FtCIOZ
a
-60
10
-
-80
40
-80
10
20
-77
30
Chem. shijl1p.p.m.
(from ext. CFCl,)
41 9.4
-118.1
-7.7
23
247
-412
-256
-274
-388
-315
-287
-262
-272
-413"
-310
Coupling constantlHz
)J(F-F)
= 421
)J(F-F) = 130
~ ( 3 5 ~ 1 -=
~ )337
(J(37c1-~) = 281
~ ( 3 5 c 1 - ~ )= 289
J(F-F)
= 443
Ref.
61
61,62
61
63
)6l
61
61
64
65
61
66
61
Only one chemical shift reported for the second-order spectrum.
been reinvestigated.6 The fundamental stretching frequencies for the most

important isotopic species were assigned and a number of 'hot' bands were
reported. The formation of BrF and I F by atom-recombination reactions in
the presence of singlet oxygen has been demonstrated and new vibrational data
have been obtained for both species.s8These results were found to support
the D;(BrF) value of 2.384 eV reported by Brodersen and Sicre. The instability
of BrF is probably responsible for the lack of attempts to prepare Lewis acidbase adducts containing this component. However, Hyman et al. have now
reported the preparation of C S B ~ F , The
. ~ ~ new compound was prepared by
62
63
g4
65
66
13'
L. G. Alexakos and C. D. Cornwell, J. Chem. Phys., 1964,41,2098.

D. Pilipovich,W. Maya, E. A. Lawton, H. F. Bauer, D. F. Sheehan, N. N. Ogimachi,
R. D. Wilson, F. C. Gunderloy, and V. E. Bedwell, Inorg. Chem., 1967, 6 , 1918.
J. Bacon, R. J. Gillespie, and J. W. Quail, Canad. J . Chem., 1963, 41, 3063.
D. Pilipovich, C. B. Lindahl, C. J. Schack, R. D. Wilson, and K. 0. Christe, Inorg.
Chem., 1972,11,2189.
K. 0. Christe and R. D. Wilson, Inorg. Chem., 1973, 12, 1356.
J. F. Mills and J. A. Schneider, Ind. and Eng. Chem. (Product Res. and Development),
1973, 12, 160.
M. A. A. Clyne, J. A. Coxon, and L. W. Townsend,J.C.S. Faraday II,1972,68,2134.
T. Surles, L. A. Quarterman, and H. H. Hyman, J . Inorg. Nuclear Chem., 1973,35,668.
43
660
Inorganic Chemistry of the Main-group Eienients
the distillation of a mixture of BrF, and Br, at 0 *C on to CsF at 197 K in

vacuo and then allowing the reaction mixture to warm up to room temperature: the residue after removing the volatiles contained 31 % CsBrF, and
69 % CsF. The Raman spectrum of the product was interpreted in terms of a
seriously distorted Dcohanion; all three fundamentals were located and a
correlation splitting was proposed for one of them.
The photoelectron spectra of bromine(v) and iodine(v) fluorides have been
obtained using He I (and He 11, for IF, only) radiation.'O Assignments were
proposed which are mutually consistent and also agree with the results reported in the same paper for SF,CI. An X-ray crystallographic investigation
of crystals of the 1 :2 adduct formed by BrF, and SbF, has shown that the
solid contains chains of discrete BrFa and Sb2Fi1 ions coupled by relatively
weak fluorine bridges (Figure 2).71This is the first direct proof of the existence
of the BrFZ ion. The co-ordination around Br is distorted octahedral with all
LFBrF close to 90"; however, highly accurate structural parameters were not
obtained
Figure 2 View in perspective of a segment of the chain structure of

[BrF:][Sb,F;]
crystals
The tetrafluoroiodate(II1) anion has now been characterized using vibrational spectro~copy.~~
The caesium salt, prepared by Christe and Naumann,
was shown to contain the D4hanion, which is thus isostructural with the other
XFh ions, X = C1 or Br, and with the isoelectronic XeF4 molecule. On the
other hand the vibrational spectrum of Cs31F, was found to be quite different
from that of CsIF,, thus excluding the formulation CsIF4,2CsF; furthermore,
the number and activity of the CsJF, absorptions rule out an octahedral
70
'l
72
R.L.DeKock, B. R. Higginson, and D. R. Lloyd, Faraday Discussions, 1972,54, 84.

M. D. Lind and K. 0. Christe, Inorg. Chem., 1972, 11, 608.
K. 0. Christe and D. Naumann, Znorg. Chem., 1973,12, 59.

661
structure for IF:-. Methyliodine(rr1) difluoride has been prepared in quantitative yield by the reaction of XeF, with excess methyl iodide at temperatures
between -40 and +20C.73 The new compound decomposes at an appreciable rate at 20 OC, and reacts slowly with glass and rapidly with mercury.
Selig and E1-Gad74have reinvestigated the I,O,-HF reaction. Using excess
anhydrous H F with either I,O, (or H1308) they were able to show by 19F
n.m.r. and Raman spectroscopythat IF, was formed. At least 30 mole HF per
mole I,O, were required to cause all the iodate lines to disappear from the
Raman spectrum. It thus seems that the overall reaction is:
with the equilibrium well over to the r.h.s. No evidence for the production of
intermediate iodine(v) oxide fluorides, such as I02For IOF,, was obtained.
Nor was there any sign of the hexafluoroidate anion in the solvolysis products
of NaIO, in HF. Although neither bromine nor chlorine reduce UF,, I2
has now been shown to do so over the temperature range 100-200 0C.75
The
equation:
312
+ 20UFs
6IFs
+ lOUaF9
was found to describe the stoicheiometry of the reaction best, Substitution

reactions on IF, have been found to be possible.76Using trimethylalkoxosilanes or dialkyl sulphites and IF, in a 1 :1 molar ratio, the reaction products
were IF,OR and Me3SiF or ROS(O)F, R = Me or Et. The two new compounds were characterized by analysis and mass spectrometry; the lgFn.m.r.
spectrum of the methoxo-derivative, a quartet at -50 ' C , is consistent with
C,, local symmetry at iodine or with a species of lower symmetry undergoing
rapid intramolecular ligand exchange.
The possible use of KrF, or KrFf salts as oxidizing agents to produce
iodine(vr1) compounds has been reported: the conversion of IF, into IF: was
effected77by KrF+ Sb2F; and Izto IF, by the neutral krypton fluoride.78
The IClf ion, which had been characterized in 1959 by X-ray crystallography, has now been studied by Raman spectroscopy as the SbCl; and
AlCI, 79 and S03F- salts, Three fundamentals, at 372, 366, and 149 cm-l,
were assigned to the C,, cation in the hexachloroantimonate salt. The
fluorosulphate analogue dissolves in HSO,F without decomposition and is
extensively ionized to give S03F- in solution.80However, Aubke et a l s owere
also able to prepare the first stable compound containing IBr$ by the action
A. Gibson and A. F. Janzen, J.C.S. Chem. Comm., 1973, 739.
H. Selig and U. El-Gad, J . Inorg. Nuclear Chem., 1973, 35, 3517.
N. S. Nikolaev, A. T. Sadikova, and V. F. Sukhoverkov, Russ. J . Inorg. Chem., 1973,
18, 751.
G. Oates and J. M. Winfield, Inorg. Nuclear Chem. Letters, 1972, 8, 1093.
D. E. McKee, C. J. Adams, A. Zalkin, and N. Bartlett, J.C.S. Chem. Comm., 1973,
26.
B. Frlec and J. H. Holloway, J.C.S. Chem. Comm., 1973, 370.
J. Shamir and R. Rafaeloff, Spectrochim. Acta, 1973, 29A, 873.
P. A. Yeats, W. W. Wilson, and F. Aubke, Inorg. Nuclear Chem. Letters, 1973,9,209.
l3
J.
74
75
76
77
78
'@
662

of Br, on iodine(1) fluorosulphate. The dibromoiodate(Ir1) cation gives only
one Raman band, at 236 cm-l, and the salt generates SO,F- ions in HSO,F
solution. The reaction of equimolar quantities of I, (or IBr) and SbCl, with
excess chlorine has been shown to produce I,Cl+ (or BrICl+) as the hexachloroantimonates in nearly quantitative yield.81 The compounds sublime at
room temperature and were shown to be partially dissociated in the vapour
state, from the mass spectra of the vapour phase in equilibrium with the
solids. The cations were also characterized by Raman spectroscopy.
The greater stability in liquid SO, of I; has been attributed to a strong
solvation effect.82 The exchange of I- with 1; in aqueous solution has been
reinvestigated by the n.m.r. line-broadening technique:s3 the new data have
resolved an anomaly in earlier interpretations. The exchange is described by
s
the reaction I- + 1, + 1, + I- at iodide concentrations greater than
0.05 moll-l. The results are said to be compatible with an attack on a
terminal iodine of I$, with the formation of 1%-as intermediate. The 0:: t
og electronic transitions (singlet and triplet) of the symmetrical trihalide ions
IXF (X = C1, Br, or I), BrF, and BrClz have been calculated in a MO
appro~imation.~~
The results were compared with the available data for
singlet-singlet transitions as well as with new data for the singlet-triplet
transitions. A distribution method for studying the stability of some unsymmetrical trihalide anions has been used to investigate the effect of the alkalimetal cation.85Potassium, as K+, was found to stabilize IIBr-, IICl-, and
BrBrC1- more effectively than either Rb+ or Cs+. As Table 2 shows, the
stability of the anions themselves increases along the series BrBrCl- <
IICl- < IIBr-.
Table 2 Thermodynamic characteristics of the unsymmetrical trihalide anions

at Z = 0.63-0.70 mol 1-1
Anionic complex
Cation AG,,,a/kcal mol-l AhHa/kcal mol-l AP/cal mol-l deg-l

K+
Rb+
cs+
K+
Rb+
cs+
K+
Rb+
cs+
a
-0.12
0.1
0.2
-0.3
-0.2
-0.2
-1.6
-1.5
-1.6
-1.6
-1.1
-1.2
0.8
0.6
0.3
-1.3
-5.0
-3.4
-0.3
-0.7
4.0
3.0
All the values were determined with an accuracy of -20 relative

81
82
83
84
-4.5
3.7
2.6
1.7
1.0
%.
J. Shamir and M. Lustig, Inorg. Chem., 1973, 12, 1108.

P. Castellonbse, G. Launay, and P.-C. Lacaze, Compt. rend., 1973,267, C, 1735.
E. E. Genser and R. E. Connick, J . Chem. Phys., 1973, 58,990.
W. Gabes and M. A. M. Nijman-Meester, Znorg. Chem., 1973, 12,589.
A. P. Mironenko, L. N. Kulikov, I. I. Alekseeva, S. B. Stepina, V. E. Plyushchev, and
L. I. Pokrovskaya, Rum. J. Inorg. Chem., 1973, 18, 656.

663
Dalziel and Aubkes6 have described the preparation of iodine-(I) and
-@I) trifluoromethanesulphonates.The latter was obtained as the sparingly
soluble product of the oxidation of iodine in CF3S03H with the stoicheiometric amount of S,06F2.The compound is thermally stable to $170 "Cand
its vibrational spectrum indicates the presence of both uni- and bi-dentate
(bridging) CF,SO, groups. The reaction of the tris-compound with I, at
140 "C results in the formation of I(OSO,CF,). Alkali-metal tetrakis(trifluoromethanesu1phonato)iodates were also prepared and their vibrational
spectra recorded.
The bis(fluorosulphato)bromate(I) in the form of its Cs+ salt had been
reported previously. A more recent investigation by Johnson and Cadys7has
shown that this anion can be generated when MS03F (M = Li, NayK, Rb,
or Cs) is dissolved in excess BrS03F. Surprisingly, the Li+ and Naf salts of
the bromo-anion could be isolated from solution but not the K+ and Rbf
salts; nevertheless, vapour-pressure measurements showed the Csf salt to be
more stable than the Li+ salt.
Bromine@ pentafluoro-orthotellurate has now been obtaineds8 by the
reaction of the chlorine analogue with Br,, thus:
2C10TeF5
+ Br,
4 CI,
+ 2BrOTeF,
The iodine(@ compound has also been reported by Seppelt:88he obtained

it by the action of CIOTeF, on ICI,. The product is stable to 180 "C but very
readily hydrolysed. The same worker has demonstrated that Br(OSeF,),
possesses appreciable acceptor properties (its 19F n.m.r. spectrum is indicative of rapid ligand exchange) and has prepared Rb+Br(OSeF,);.
Dimethylbromonium hexafluoroantimonate is a particularly stable halonium salt which promises wide application as a selective methylating agent.
It can be prepared in nearly quantitative yield by the reaction of excess methyl
bromide and a 1:1 mixture of HF and SbF, at -20 0C.89
Oxide Halides.-"he attempted preparation of F,ClO+ from F3C10 and PtF,
and from F3CIO-F,-SbF, was unsuccessful however, Christe points out
that the possibility of preparing the pseudo-octahedral F,CIO molecule
cannot be ruled out. The I0F n.m.r. spectra of the known, stable, chlorine
oxide fluorides and their related cations have been reported by Christe
et al. their data are shown in Table 1 . Details of the synthesis, purification,
and properties of F3C102have been reported by Christe and Wilson.66The
compound melts at -81.2OC and has an extrapolated boiling point of
-21.6 "C; it is marginally stable in a well-passivated system at ambient
temperature. The single IgFn.m.r. signal at -413 p.p.m. was interpreted as
an AB, multiplet; of the two possible isomers (1) and (2) with C,,symmetry,
only model (1) was said to be consistent with the vibrational spectrum. It
86
J. R. Dalziel and F. Aubke, Irrorg. Chem., 1973, 12, 2707.

W. M. Johnson and G . H. Cady, Znorg. Chem., 1973, 12, 2478.
G. A. Olah and J. J. Svoboda, Synthesis, 1973, 203.
664

F
I /o
F-Cl
INo
F
I I ,F
o=c1
FI '
F
forms ionic adducts stable at 25'C with strong Lewis acids such as BF,,
AsF,, or PtF5.90The greater stability at 20C of the BF; salt as compared
with that of CIOiBF, was used in the purification of F,CIO,, which was
regenerated from the purified F2CIOiBF,- by treatment with FN02. The
vibrational spectrum of F2C102, as its BFy, AsF;, and PtF- salts, has been
compared with that of the isoelectronic S02F2.The i.r. and Raman spectra of
F,C102 have been obtained and the twelve fundamentals have been found to
be consistent with C,,symmetry.91The spectra in condensed phases show only
minor frequency shifts compared with those from the gas and are thus indicative of little or no intermolecular association; this conclusion is in complete
agreement with other physical properties of the compound. This finding is
somewhat surprising since both CIF, and F,ClO show a pronounced tendency
to associate in the liquid and solid states through bridges involving the axial
fluorines.
The force constants of the perhalyl fluorides FXO, (X = Clg2or BrQ2sg3)
have been calculated. The bond orders obtained reflect the greater stability
of the ClV1I state compared with that of BrVI1. Additional experimental
evidence for violet and blue compounds containing chlorine, oxygen, and
fluorine has appeared;94Gardiner has suggested that the most likely structure
of the violet compound is F,ClO,F, whereas the blue compound may be
F2C1O2C1F2.Schack et aLg5have investigated some reactions of the recently
discovered halogen perchlorates C1,04 and BrCIO,. They have been found to
react with perhalogeno-olefins by adding across the double bond. These
reactions proceed quickly at low temperatures, in the absence of a solvent, to
produce the previously unknown (and surprisingly stable) perhalogenoalkyl
perchlorates in high yield. Compounds prepared in this way include
ClCF2CFClC104,BrCF,CFCl.CIO,, and CF,CFBrCF2CI04. Reactions
of these perhalogenoalkyl perchlorates with ionic fluorides were found to
produce the corresponding acyl fluoride.
Compounds with Oxygen.-From photoionization mass spectrometry of F20
it has been deducedg6that the adiabatic first ionization potential is at 13.11 f
0.01 eV and also that the appearance potential of O F (OK) has an upper
limit of 14.44 eV, which is considerably less than the electron-impact value
of 15.8 eV. These results imply that AHto (OF) = 26.1 f 2.3 kcal mol-l and
go
B1
O2
93
94
95
96
K. 0. Christe, R. D. Wilson, and E. C. Curtis, Inorg. Chem., 1973, 12, 1358.

K. 0. Christe and E. C. Curtis, Znorg. Chem., 1973, 12, 2245.
S. P. So and F. T. Chan, 2.phys. Chem. (Frankfurt), 1973, 85, 69.
E. J. Baran and P. J. Aymonino, 2.Naturforsch., 1972,27b, 1568.
D. J. Gardiner, J. Fluorine Chem., 1973, 3 , 226.
C. J. Schack, D. Pilipovich, and J. F. Hon, Inorg. Chem., 1973, 12, 897.
J. Berkowitz, P. M. Dehmer, and W.A. Chupka, J. Chern. Phys., 1973,59.925.

665
I.P.(OF) = 12.79 f 0.10 eV. Russian workersg7have investigated the reaction
of F2 and 0, in a Pyrex reactor under the influence of a silent electric discharge. The reaction products were oxygen fluorides with 0 :F ratios in the
range 1.2-2.04; the experimental conditions were varied widely to see what
effect they had upon this ratio,
Czarnowski and SchumachergEQ
have investigated the kinetics of the thermal
decomposition of F,O using a static method. The temperature was varied
between 501 and 583 K and the total pressure between 10 and 750 Torr. The
reaction was shown to be homogeneous and essentially of second order at
moderate and higher pressures. The following mechanism was proposed to
explain the results :
FZO
+ FZO -+ + FO* + FZO

F a
+ FzO + F2 + FO*
F* + F* + F,O
Fa + FzO
FO* + FO* -+
+ 2F*
F*
--j
0 2
The stepwise dissociation energies D(F0-F) and D(0-F) were calculated

from the data as 40 f 1 and 50.8 f 2.0 kcal. These are in excellent agreement
with the recent figures obtained by Clyne and Watson?8b H o u ~ e has
r~~~
expressed scepticismfor the kinetic data for this pyrolysis reaction as deduced
from the shock-tube experiments of Lin and B a ~ e r Houser
. ~ ~ ~ places more
trust in the kinetic data obtained from earlier studies using conventional
techniques.
AppeImanloohas reviewed the case history of HOF, the recently isolated
non-existent molecule, which may well be the reactive species formed when
F, reacts with water. The photoelectron spectrum of this unstable compound
has been obtained by Berkowitz et aZ.lol using He I resonance radiation.
Three bands were observed which could be interpreted by analogy with the
diatomic halogens and with the recently reported CIF. The first (adiabatic)
ionization potential was found to be 12.69 -+ 0.03 eV, in close agreement with
the photoionization value of 12.7 f 0.01 eV.
The microwave spectrum of the BrO. radical in the first excited vibrational
level of the ground electronic state has been observed and analysed.lo2A
re-analysis of the vibrationally unexcited radical has given re = 1.717 f
0.001 A. The Raman spectrum of solid BrO, at -180 O C has been interpreted
in terms of the dimeric structure Br,O, containing a Br-Br bond.lo3 Pascal
s7
I. V. Nikitin, A. V. Dudin, and V. Ya. Rosolovsky, Izvest. Akad. Nauk S.S.S.R.,
Ser. kkim., 1973, 269.

( a ) J. Czarnowski and H. J. Schumacher, Chem. Phys. Letters, 1972,17,235; (6) M. A.
Clyne and R. T. Watson, ibid., 1971,12, 344.
sQ (a) T. J. Houser, J. Amer. Chem. SOC.,1973,95, 1389; (b) M. C. Lin and S. H. Bauer,
ibid., 1969, 91, 7737.
loo E. H. Appelman, Accounts Chem. Res., 1973, 6 , 113.
lol J. Berkowitz, J. L. Dehmer, and E. H. Appelman, Chem. Phys. Letters, 1973,19,334.
loZ T. Amano, A. Yoshinaga, and E. Hirota, J . Mol. Spectroscopy, 1972,44,594.
lo3 J.-L. Pascal and J. Potier, J.C.S. Chem. Comm., 1973, 446.
Q8

and Potier observed five groups of lines, including a very strong sharp band
at 205 cm-l which they assigned to the Br-Br stretching vibration; the
analogous vibration in Br, occurs at 300 cm-l. These conclusions point to an
intriguing trend for the halogen dioxides : ClO,-monomer; Br0,-dimer ;
102-oxygen-bridged dimer.
The oxidation of NaClO, and the reduction of C102in DMSO at platinum
and vitreous carbon have been studied electrochemically.104It was shown that
the primary step in each process is a one-electron transfer and that this is
followed by a complex reaction involving CIOz and ClO;. The spectrum of a
transitory species has been observed (just after the flash) in the photolysis of
CIOz in aqueous s01ution.l~~
This spectrum was attributed to CI2O2: two
possible structures were proposed for the transient, namely Cl-0-Cl-0
or Cl-C102, which could be produced by the reaction of Cl (or Cl;) with
ClOZ.
Nikitina and Rosolovskylo6have examined the reactions between chlorine
oxides and the Lewis acids Al,Cl, and SbF,. The ClZ06-Al,Cl, reaction has
been studied both without and with a solvent (SO2 or C102).foCa
All the
chlorine on aluminium could be displaced using excess C120,; A1(C104)s,C1206,
prepared in this way, was characterized by i.r. spectroscopy and hence
described by the formula ClO~[Al(ClO,),]-. It decomposes at 90 "C in vacuo
to aluminium perchlorate. The interaction of Cl2O, ClO,, and Cl,O, with
SbF, has been shown to produce ClOz salts with fluoroantimonate(v)
anions.loob
South African workers have investigated the stability and reactivity of the
HgO-I, reagent.lo7In its reactions with alcohols the rate-controlling step is
the rate of formation of the 'positive iodinating species'. The rate at which the
latter decomposes, thermally and photochemically, was examined; it was
found that the rate of reaction with alcohols at 54C competes favourably
with that of thermal decomposition. Furthermore, irradiation at 0 "C
effectively increases the rate of reaction with diols.
Siebert and co-workerslo8have investigated the reactions and spectroscopic
properties of a number of orthoperiodates. They were able to characterize the
hexahydroxoiodine(vI1) cation by Raman spectroscopy.losa Solutions of
HJO, in 95 % sulphuric acid yielded crystals of composition H,IO,,H,SO,,
which they formulated as I(OH)$HSO,. At temperatures above 120 "C such
solutions decompose to 0, and precipitate I2OS. The vibrational spectra of
H,I06 and of a number of salts containing the 10;- ion were also reported and
assigned:loBb
they inferred that n-bonding is quite extensive in this anion. An
666
J. Bessard and G. Cauquis, Bull. SOC.chim. France, 1973, 1936.

J. C. Mialocq, F. Barat, L. Gilles, B. Hickel, and B. Lesigne, J. Phys. Chem., 1973,77,
742.
lo6 (a) Z . K. Nikitina, A. K. Karelin, and V. Ya. Rosolovsky, Izvest. Akad. Nuuk S.S.S.R.,
Ser. khim., 1973, 723; (6) Z . K. Nikitina and V. Ya. Rosolovsky, ibid., p. 273.
lo' C. P. Forbes, A. Goosen, and H. A. H. Laue, J. S. African Chem. Inst., 1972,25,328.
lo* (a)H. Siebert and G. Wieghardt, 2.Nuturforsch., 1972,27b, 1299; (b) H. Siebert and
U. Woerner, 2.anorg. Chem., 1973, 398, 193.
lo4
lo6
667
incoherent-neutron-scatteringstudy of hydrogen-bonding in paraperiodic and

iodic acids has led to the conclusive assignments of vibrational modes involving motion of hydrogens.lo9 This in turn has led to a reinterpretation
of the 1-0 vibrations in these acids. The crystal structure of K,IO,, potassium mesoperiodate, can be considered to be related to (NH,),FeF, with the
tetragonal pyramidal 10;- anion replacing FeF:.l0
The co-ordination of the
anion is such that the OapicalIOangle is about 95.
Freshly precipitated hydrated Ge02 dissolves in aqueous iodic acid, and
the addition of MN03 (M = NH,, K, Rb, or Cs) results in the precipitation
of M2[M(I03),] (M = Ge), which is isomorphous with the series of compounds with M = Sn, Pb, Ti, Zr, or Mn.ll1 The crystal structure of
K2Ge(103)6was investigated; it contains Ge octahedrally co-ordinated by the
oxygen atoms of six pyramidal 1 0 3 groups. Balicheva and Petrova have
examined the effect of the cation on the vibrational modes of the 10; ion in
alkali-metal and ammonium iodates.l12 The LiIO3-HIO3-H,O system at
50C has been investigated and the three ranges have been identified in
which LiIO,, HIO,, and a solid solution of these two components crystallize
0 ~ t . l ~ ~
Appelman has reviewed the present state of our knowledge of the perbromate ion.loOIn collaboration, he investigated the effect of pulse radiolysis on
aqueous solutions of KBrOp.l14 It was found that BrO, reacts with the hydrated electron according to:
BrO;
+ eiq
BrO?
+ 0-
The second-order rate constant for this process was determined. A polarographic study of the reduction of perbromate ion at mercury has confirmed
that the reaction rate is not affected by hydrogen ion concentration for pH
values less than 12.115These authors were able also to investigate the effect of
the double-layer structure upon BrOh electroreduction.
The reaction between bromate and iodide:
BrO;
+ 91- + 6H+
Br-
+ 31; + 3H,O
has been followed spectrophotometrically in DMSO-water mixtures.l16

Catalysis by added C1-, Br-, and NCS- was detected; the proposed mechanism involves protonation of BrO; followed by the (rate-determining) attack
by the nucleophilic anion on the H2BrO+species. In a solvent containing more
loo
F. P. Temme, T. C. Waddington, L. V. Jones, and J. A. S. Smith, Nature Phys. Sci.,

1973, 241,40.
H. Dolling and M. Tromel, Naturwiss., 1973, 60, 153.

R. Frydrych, F. Schellhaas, and Ch. Pflugmacher, 2. anorg. Chem., 1973,399, 73.
lla
T.G. Balicheva and G. A. Petrova, Zhur. strukt. Khim., 1973, 14,463.
113 L. A. Azarova, E. E. Vinogradov, E. M. Mikhailova, and V. I. Pakhomov, Russ. J .
Inorg. Chem., 1973, 18, 124.
114 K. J. Olsen, K. Sehested, and E. H. Appelman, Chem. Phys. Letters, 1973, 19,213.
115 D.Cozzi, M.L. Foresti, and R. Guidelli, J . Electroanalyt. Chem. Interfacial Electrochem., 1973, 42, App. 31.
116 J. H. Krueger and T. R. Webb, Inorg. Chem., 1973, 12, 1587.
ll1
668

than 0.7 mole fraction DMSO the order of nucleophilic reactivity is C1- >
Br- >I-. C102 and ClO, are the oxidation products of the bromatechlorous acid rea~ti0n.l~'
The kinetics of the reaction have been studied in
the presence of ally1 alcohol, to scavenge the hypobromous acid intermediate
and simplify the kinetics. The kinetics of the reaction between Br-- and excess
BrO; in aqueous acid are known and the bromine generated has been found
to account for the autocatalytic part of the Fe(CN):--BrO;-H+
reaction.l18
The other part of this redox reaction contains both a 'normal' [H+I2path as
well as a path independent of pH. These observations have been tentatively
interpreted in terms of parallel inner- and outer-sphere paths. The results
from the Fe;&,-BrO;-H+
reaction provide definite evidence for the occurrence of an inner-sphere path, probably involving substitution on Fe2+
rather than on BrO;.l19 The oxidation of neptunium ions by bromate in acid
solution is one step in a commonly used purification cycle for neptunium.l20
Part of the reaction system has now been investigated in detail and the kinetics
have been reported by Knight and Thompson.
The crystal structure of HC10,,3$H20 at - 188 OC has been determined.121
The structure takes the form of a three-dimensional hydrogen-bonded network, of water molecules and oxonium ions, which may be described as two
independent H,Or ions sharing a common H20. The two independent ClO;
ions also participate in the hydrogen-bonding to a limited extent so that they
exhibit only minor deviations from tetrahedral symmetry. Grigorovich et
~ 1 . have
l ~ ~ investigated the interaction between ionic perchlorates in anhydrous
HC104, both with and without the addition of chloroform, by l H n.m.r. A
linear relationship was noticed between the downfield chemical shift and the
concentration of MCIO, (M = K, Rb, Cs, or Bu,N). Pure perchloric acid
reacts slowly with graphite at room temperature giving graphite perchlorate,
a first-order intercalation compound, and C103?23Dichlorine heptoxide,
either as the liquid at -20 "C or in the vapour phase, also reacts with graphite, and the product CI2Cl20,was obtained.
The eutectic solvent HCI0,-H20 is especially suitable for Salzkryoskopie
of cations which are stable only in acid solutions and of acids.124With the
latter the depression of freezing point is not affected by the degree of acid
dissociation. On the other hand, polymerization of the acid molecule (or its
dissociated anion) will lead to a decreased freezing-point depression. Solutions
of nitric acid in this medium have been reported to produce anomalously low
depressions, indicative of dimer formation. The available data are not adequate to distinguish between such species as H2N206,HN20;, N,OZ-, or
R. C. Thompson, Inorg. Chem., 1973, 12,1905.
J. P. Birk and S. G. Kozub, Inorg. Chem., 1973, 12,2460.
J. P. Birk, Inorg. Chem., 1973, 12, 2468.
120 G. C. Knight and R. C. Thompson, Inorg. Chem., 1973, 12, 63.
121 J . Almlof, Chernica Scripta, 1973, 3, 73.
122 Z. I. Grigorovich, Yu. I. Malov, and V.Ya. Rosolovsky, Izvest. Akad. Nauk S.S.S.R.,
Ser. khim., 1973, 265.
123 H. Fuzellier and A. Herold, Compt. rend., 1973, 276, C, 1287.
lZ4 M. Ardon and L. Halicz, Inorg. Chem., 1973, 12, 1903.
11'
11*
669
even N206, nor was the thermal stability of the species established. The
thermal decomposition of molten M11(C104)2 (M = Cu, Mn, Fe, Co, or Ni)
in an argon atmosphere has been investigated by t.g.a. and d.t.a. techniques.126
The reaction products were shown to be metal chlorides and, less commonly,
oxides.
A study of the interaction between anhydrous HClO, and acetonitrile has
revealed that a gradual ionization of the 1 :1 complex initially formed takes
place:126this behaviour was compared with that for the CH,CN-HX systems
(X = Cl, Br, or I). Acetic acid and acetone were said to undergo extensive
protonation in the CH3CN-HClO, system. The equilibrium constant for the
formation of the 1 :1 complex between nitromethane and perchloric acid has
been determined by i.r. spectrometry over the temperature range -20 to
+25 OC:12' the enthalpy and entropy changes for the reaction are -6.6 f
0.7 kcal mol-l and 11 f 2 cal mol-l deg-l.
Mixed crystals of NaC103-NaBr0, do not exhibit a linear change in the
cubic cell constant with composition.128The i.r. spectra, at room temperature
and at -196 'C, of pure NaClO, and of NaClO, in a NaBrO, matrix provide
further evidence of intermolecular coupling. However, additional effects
influence the spectrum of BrO; in NaBrO, and in a NaClO, matrix.
A revised procedure has been given for the standardization of iron(@
solution with potassium ~ h l 0 r a t e . l ~ ~
Hydrogen Halides.-An introduction to chemical lasers by Kompa,130 giving
due emphasis to those based on the hydrogen halides, reviews the literature
up to Spring 1972 and examines some current concepts and perspectives in
order to point out possible directions for future developments in this field.
Numerous references to studies of vibrational relaxation in the gaseous hydrogen halides have been located.90131J32 Thus Hinchen131 has compared the
ratio of relaxation rates of HX/DX, where X = F, C1, or Br. He pointed out
that the relaxation rates for H F and DF are orders of magnitude faster than
for the other HX molecules; although theoretical treatment of these rates is
in fair agreement with experiment, there are still serious defects in the theory.
The enthalpy of solution of a-quartz (or low quartz) in aqueous hydrofluoric acid has been determined under standard conditions in order to
provide a reference standard for H F solution ca10rimetry.l~~Kresge and
Chiang have investigated solvent (H20 and D20) isotope effects on the
R. Vilcu and N. Georgescu, Rev. Roumaine Chim., 1972, 17, 1791.
M. Kinugasa, K. Kishi, and S . Ikeda, J. Phys. Chem., 1973,77, 1914.
C . Belin and A. Potier, J. Chim. phys., 1973,70, 490.
Ia8 W. Sterzel and U. Knoll, Z. anorg. Chem., 1973,399,25.
C. Trichk, Z. analyt. Chem., 1973,265, 348.
130 K. L. Kompa, Topics Current Chem., 1973,37, 1.
131 J. J. Hinchen, J. Chem. Phys., 1973,59, 233.
132 (a) J. L. Ah1 and T. A. Cool, J. Chem. Phys., 1973,58, 5540;(b) K. G. Anlauf, P.H.
Dawson, and J. A. Herman, ibid., p. 5354;(c) J. F. Bott and N. Cohen, ibid., p. 4539;
( d ) G.C.Berend and R. L. Thornmarson, ibid., pp. 3203,3454.
ls3 M.V. Kilday and E. J. Prosen, J. Res. Nut. Bur. Stand., Sect. A , 1973,77,205.
125
12*
670
ionization processes of aqueous HF:

HF
+ H,O + H,O+ + F-
and
HF
+ F- + HF;
and have compared the result of their own calculations with experimental
data.134
The lH and 19Fn.m.r. chemical shifts of mixtures of HF and SO2have been
studied as functions of concentration and temperature.135The results obtained
from dilute HF solutions were used to calculate a value of 6.29 kcal mol-l for
the enthalpy change in the reaction 2HF-t (HF),. On the other hand, the
shifts produced on the addition of electrolytes MF, MBF,, MAsF,, and
MSbF, to pure H F were interpreted in terms of ionization and solvent
depolymerization effects. A new determination of the couples Pt/H,(HF) and
Ni/F,(HF) at 25 "C has been made by Mougin and Royon13using a reference
cell based on the Hg/Hg,F2 couple. The values obtained, -0.58 and +2.25 V,
respectively, are in agreement with accepted values and confirm the exceptional
ability of pure H F to resist oxidation.
have reported that a 1 :1 mixture of HF and SbF5is one of the
Olah et
most effective 'superacid' media in catalysing hydrogen-deuterium exchange
in H,-D, mixtures. The mechanism proposed for the reaction involves the
protonation of hydrogen to form the unstable Hg intermediate in solution.
Olah and Shen2' have found that addition of Cl,, Br2, COZY
and Xe suppressed
this scrambling reaction - under comparable conditions the percentage suppression was 94,94, 33, and 30%, respectively. On the other hand N2 and 0,
were found to have no such effect on the H,-D, reaction. These facts were
interpreted on the basis of the degree of protonation (and solubility) of these
very weak bases in this superacid. Gillespie and Hulme13' have produced
evidence to show that HCN is protonated by HF in the presence of BF, or
AsF,. Unstable solids, believed to be HCNH+BF;;(AsF;), have been prepared. In addition, they were able to confirm that solutions of HCN in HF
are slowly solvolysed, forming the cation F,HCNHZ, which they isolated as
the AsF; salt. Christe et aL61 have observed that solutions of CIF,AsF, and
ClF,OAsF, in liquid HF exhibit characteristic 19F n.m.r. spectra of the
AsF; ion: the cation resonance was assumed to have merged with that of the
solvent. However, on the addition of excess AsF, the cation resonances
appeared while the AsF; resonance merged with that of the solvent.
The surface tension of the NH,-HF system has been measured as a function
of the temperature and of the composition in the range of composition 78134
135
136
13'
A. J. Kresge and Y . Chiang, J. Phys. Chem., 1973, 77, 822.

J. Shamir and A. Netzer, Canad. J. Chem. 1973, 51, 2676.
G. A. Olah, J. Shen, and R. H. Schlosberg, J. Amer. Chem. SOC.,1973, 95, 4957.
R. J. Gillespie and R. Hulme, J.C.S. Dalton, 1973, 1261.

671
86 weight % HF.138 Using an accurate transpiration method, no reaction
could be detected between AIF, and HF at temperatures near to 1200K
using pressures of HF less than 1 atm.139
Experimental and theoretical data for the hydrogen difluoride ion have been
combined so as to fit a newly proposed model for the linear symmetric
hydrogen-b0nd.1~~
However, Williams and Schneemeyer141have reported an
asymmetric single-minimum hydrogen bond in the anion of p-toluidinium
HF,. These authors suggest that the well-known symmetric hydrogen bond
only arises whenever the combined electronic and crystal environment about
an ion lacks sufficient asymmetry to distort the potential surface experienced
by the bridging proton. This and the results derived from the study of very
short O-H. * .O bonds suggest that regardless of the shortness of the
X-(H)-X
distance, the molecular geometry of the hydrogen bond is
strongly dependent on the near-neighbour geometry. Further refinement has
been carried out on the neutron-diffraction data for KHF,.142 The best
agreement was obtained for a physically impossible model, which also had
to be rejected on other grounds. A combination of spectroscopic and diffraction data for MHF, (M = Na, K, or NH,) was used in a detailed analysis
of the thermal motions: the average F-(H)-F
distance was found to be
2.292 f 0.0048, after correction.
Ionic conduction has been shown to occur in MHF, (M = K, Rb, or Cs)
in both the ct (tetragonal) and the P(cubic) phases.14, Plots of the zerofrequency conductivities uersus T-l show discontinuities at the ct-p transition
temperatures: moreover, the gradients for the phases are all essentially the
same (AE 20 kcal), whereas there are considerable differences between the
gradients for the low-temperature ct phases.
The i.r. spectra of the H,O,HCl complex, in a nitrogen matrix at 15 K,
strongly indicate that the complex involves a hydrogen bond much like that in
the Me,O,HCI complex, rather than a full proton transfer, as in H,0+C1-.144
The influence of the matrix is, therefore, thought to be very important. A
detailed study by Bertie and Falkf45of the i.r. spectra of Me,O,HCI and of
some of its isotopic modifications in the gas phase has provided assignments
of the vibrational modes of the hydrogen bond.
HBr is known to inhibit combustion of hydrogen and hydrocarbon fuels
and it is generally accepted that the inhibition results from reactions of HBr
with the chain centres which are important for flame propagation, e.g. H.
and OH. radicals. Takacs and Glass146have now investigated the absolute
138
140
141
142
lP3
144
145
146
F. Breda and M. Rolin, Bull. SOC.

T. B. Douglas and R. F. Krause, J. Res. Nat. Bur. Stand. Sect. A, 1973, 77, 341.
G. J. Jiang and G. R. Anderson, J. Phys. Chem., 1973, 77, 1764.
J. M. Williams and L. F. Schneemeyer, J . Amer. Chem. SOC.,
1973,95,5780.
H. L. Carrel1 and J. Donohue, Israel J. Chem., 1972, 10, 195.
J. Bruinink, J . Znorg. Nuclear Chem., 1973, 35, 1698.
B. S. Ault and G . C. Pimentel, J. Phys. Chem., 1973, 77, 57.
J. E. Bertie and M. V. Falk, Canad. J . Chem., 1973, 51, 1713.
G. A. Takacs and G . P. Glass, J . Phys. Chem., 1973,77,1060,1182,1948.
612
rate constants for the processes:
+ HBr Hz+ Br.

OH* + HBr
H20 + Br.
0. + HBr -+ OH- + Br.
H-
-+
in a fast discharge flow apparatus and using e.p.r. detection. The same
workers also studied the reaction of hydroxyl radicals with HCl and HI.
The rate constants for the reactions :
OH-
+ HX -+ H 2 0 + X
(X = C1 or I)
were also determined and were found to form a reasonable pattern when the
datum for the analogous HBr reaction was included,
The kinetics of the oxidation of aqueous HBr by nitric acid in the presence
of HNOz have been reinvestigated.14A mechanism was proposed which is
based on fast equilibria forming an intermediate, which reacts further in a
slow stage. Nitryl bromide was put forward as this intermediate as an alternative to N,O,Br. The equilibria are reversed at high water concentrations
and this effect has been used to estimate the hydration numbers of salts,
The i.r. spectra of HI and DI were determined in a number of different
matrices and in the solid phase at 20K, and revised assignments of the
multimer absorptions were proposed.148
2 Hydrogen
Protonic Acid Media.-As with last years Report the coverage in this section
is incomplete, and more information will be found under those headings
dealing with the individual acids.
G i l l e ~ p i e has
l ~ ~reviewed
~
the chemistry in superacid systems and dealt
with such topics as acidity functions, protonation reactions, and the formation of novel cationic species (see also ref. 149b). Additional Hammett
acidity function data, H,, have been measured for a number of solutions in
fluorosulphuric acid using a set of aromatic nitro-compounds as i n d i ~ a t 0 r s . l ~ ~
The results show conclusively that HS0,F is a stronger acid than H,SO,. The
incremental addition of SbF, or SbF5,3S03 to HSO,F causes a very steep
rise in the acidity of the medium. Some of the results are listed in Table 3.
Mixtures of H2 and D, have been found to undergo exchange reactions
with the formation of HD in a number of superacidsat room temperature.136
Feilchenfeld, S. Manor, and J. A. Epstein, J.C.S.Dalton, 1972, 2675.
A. J. Barnes, J. B. Davies, H. E. Hallam, and J. D. R. Howells, J.C.S. Furuday ZZ,
l.i7 H.
148
140
1973, 69, 246.

(a) R. J. Gillespie, Endeuoour, 1973,33, 3 ; (b) R. J. Gillespie, Halogen Cations in
MTP International Review of Science, Inorganic Chemistry Series One, Vol. 3, p.
199, ed. V. Gutmann, Butterworths and Univ. Park Press, 1972.
R.J. Gillespie and T. E. Peel, J. Amer, Chem. Soc., 1973, 95, 5173.
673
Table 3 No Values for some anhydrous protonic acids

Acid
--Ho
H2SO4
HzSz07
HS03F
HSOsF-(5 % AsF,)
HS03F-(5 % SbF,)
HSO,F-(5 % SbF5,3SOs)
11.93
14.14
15.07
16.61
18.28
19.10
The 'superacid' systems investigated were, in order of their ability to catalyse

the scrambling reaction, HF-SbF, >HSO,F-SbF, > H,SO,-SbF,.
The
mechanism put forward for the reaction involves the protonation of H, to
form HZ in solution. Olah and Shen2' also reported evidence for the protonation of CI,, Br2, CO,, and Xe in HF-SbF,. Rode and Engelbrecht151have
compared experimental pK values for protonic acids HX in water and in
glacial acetic acid with the proton affinity of X-, as calculated by the CND0/2
method. Their results are shown in Figure 3. However, proton charge densities, calculated by the same authors, did not correlate satisfactorily with
experimental pK values.
Hydrogen-bonding.-The
hydrogen ion complex [H(napht),]+ (napht =
1,8-diazanaphthaIene) has been isolated as its perchlorate salt.152The crystal
610
S70
530 490
450
-8.0 -6.0 -4.0 -2.0
0.0
2.0
4.0
6.0
0.0
10.0 12.0
PK
Figure 3 Proton afinity (P.A.) of X-plotted against the PK value of acid HX

in ( a ) H 2 0 and (b) MeC0,H
(Reproduced by permission from Monatsh., 1973, 104, 893)
161
162
B. M. Rode and A. Engelbrecht, Monatsh., 1973, 104, 893.

M. Bacci, A. Dei, and R. Morassi, Znorg. Chim. Acta, 1973,7,209.

structure of dipyridinium octafluoro-di-poxo-diarsenate has been determined;153 the cation-anion interaction is uia hydrogen bonds between the
pyridinium ions and the bridging oxygen atoms (N-H. - .Odistance 2.86 A).
Thomas154has obtained the photoelectron spectra of dimers and mixed complexes of carboxylic acids using a spectrometer with a cooled target chamber.
It was found that the ionization potential of an electron from a non-bonding
orbital on the proton-donor group is decreased whereas that on the electronpair-donor group is increased. The association between CH,CI,,CO,H
(n = 0, 1, or 2) and a series of sulphoxide, selenoxide, and phosphine oxide
bases has been investigated by measuring the absorbance of ~(0-H) of the
free a ~ i d . 1The
~ ~association constants and thermodynamics of association
were derived from these data. A linear relationship was found between
AH&^^^ and the pK, of the acids. The strongest hydrogen bond is formed between CCl,CO,H and Ph,SeO, - A H o
67 kJ mol-l. Had% et aZ.156have
also investigated the i.r. and Raman spectra of crystalline NaH(CH,COO),
KH(CF,COO),, and KH [(CH,COO),] and of their deuteriated analogues in
the range 4000-30 cm-l. These acid salts contain crystallographically symmetric and very short hydrogen bonds and, on the basis of this new spectroscopic evidence, the hydrogen bond is indeed of the symmetric singleminimum type.
An incoherent-neutron-scattering study of hydrogen-bonding in paraperiodic and iodic acids has produced useful information on the frequencies
of the OH modes of both acids.loSA correlation of y(OH) frequencies with
their O-(H). * -0distances was produced. A neutron-diffraction refinement
of the structure of the monoclinic modification of Te(OH)6 has given the
hydrogen-bond parameters with high accuracy.157 The O-H bonds range
from 0.977 to 0.990 A and the mean O-H. - -0angle in the hydrogen bond
is 173.6'.
More recent results from the theory of hydrogen bonds and proton-transfer
processes have been reviewed by S c h u ~ t e r Ab
. ~ ~initio
~ LCAO SCF calculations have been performed on the 1 : 1 adduct of HCN and HF, in which
HCN functions as the proton-acceptor molecule.15s The predicted equilibrium
geometry is linear, FH- .NCH, and is well described by the general hybridization model for the hydrogen bond. Del Bene160has published the results of
ab initio SCF calculations on the series of dimers ROH- - .NH,, where
R = H, Me, NH,, OH, or F. These dimer structures also fit the general
hybridization model.
674
153
l5*
156
15'
158
lSD
I6O
W. Haase, Chem. Ber., 1973,106, 734.
R.K.Thomas, Proc. Roy. SOC.,1972,331, 249.

D. HadZi and I. Rajnvajn, J. C. S. Furuduy I , 1973,69, 151.
D. Hadti, B. Orel, and A. Novak, Spectrochim. Acta, 1973,29A, 1745,
0.Lindqvist and M. S. Lehmann, Acta Chem. Scand., 1973,27,8 5 .
P. Schuster, 2. Chem., 1973,13, 41.
J. E. Del Bene and F. T. Marchese, J . Chem. Phys., 1973,58, 926.
J. E. Del Bene, J. Amer. Chem. SOC.,1973,95,5460.
675
Miscellaneous.-A theoretical discussion of the binding energy and geometry

of the hydrogen ion clusters, H:, has been given by Harrison et aZ.161 The
structures proposed are related to the triangular HZ by the addition of
successive H, units.
The nucleophilic reactivity of H- for substitution at CH,Cl, HCH,Cl--+ CH4 C1-, has been determined quantitatively in the gas phase
using the flowing afterglow technique :47 comparisons were made with other
gas-phase basicities.
161
44
S. W. Harrison, L. J. Massa, and P. Solomon,Nature Phys. Sci., 1973,245,31.
The Noble Gases

BY
M. F. A.
DOVE
1 The Elements
Calculations of vibrational and rotational level spacings of Ar2, Kr2, and
Xe2 have been performedl on the basis of accurate fits to molecular-beam
scattering data. Evidence has been reported2a for the stabilization of protonated argon molecules in a solid argon matrix at 14 K. The 905(644) cm-l
i.r. absorption of the products of both the glow discharge experiments on
Ar-H,(D2) and the 1216 A photolysis experiments on numerous hydrogenatom sources in argon matrices can most reasonably be assigned to H(D)Ar:.
The value of n is as yet indeterminate. Olah and Shen2bhave proposed that
elemental xenon is partially protonated in HSbF,: their evidence was based
on the effect of xenon on the isotopic scrambling reaction of D, in HF-SbF,
solution.
The observation of XeCl- in the gas phase at lo-* Torr has been ~ l a i m e d . ~
The ion was generated in a conventional ion-cyclotron resonance spectrometer by means of the reaction COClXe+ XeClCO. The dissociation energy of XeC1- into Xe and C1- was estimated to be less than
10 kcal mol-l. However, ab initio electronic-structure calculations4 on the
lowest ,X+ and 211 states of XeF suggest that this is not a chemically bound
species in the gas phase.
An oxidation method for removing radon from gas mixtures by means of
the reaction with liquid BrF, has been tested5 using samples containing
amounts of the order of 0.2 pCi 1-1 of 222Rn.The possibility of purifying air in
uranium mines with BrF, and other oxidizing agents was discussed.
2 Argon, Krypton, and Xenon(I1)

The molecular structure of the unknown argon@) fluoride has been predicted6from that of the formally analogous Me,PF2; the Ar-F bond length
K. K. Docken and T. P. Schafer, J. Mol. Spectroscopy, 1973,46,454.
( a ) D. E. Milligan and M. E. Jacox, J . Mol. Spectroscopy, 1973,46,460;(b)G . A. Olah
and J. Shen, J . Amer. Chem. SOC.,1973, 95, 3582.
J. M. Riveros, P. W. Tiedemann, and A. C. Breda, Chem. Phys. Letters, 1973,20,345.
D. H. Liskow, H. F. Schaefer, P. S. Bagus, and B. Liu, J. Amer. Chem. SOC.,
1973,95,
4056.
L. Stein, J. Inorg. Nuclear Chem., 1973, 35, 39.
H. Yow and L. S. Bartell, J. Mol. Structure, 1973, 15, 209.
676
The Noble Gases

677
is expected to be approximately 1.76 A. The He I1 photoelectron spectra of
KrF, and XeF, are still controversial subjects. Further criticism has appeared'
of the assignments of the weak, broad bands between 22 and 23 eV for both
molecules. DeKock prefers to assign them to electronic states and suggests
that they obtain their intensity through configuration interaction.
Three adducts of KrF,, viz. KrF,,TaF, and KrF2,2MF, (M = Nb or Ta),
have been prepared by Frlec and Holloway.* The reactions were carried out
in liquid BrF, at -27 OC. The 1 :1 adduct loses TaF, in vacuo and the 1 :2
adducts themselves are less stable than the analogous KrF,,2SbFs. No 2: 1
adducts could be prepared although some spectroscopic evidence for the
existence of Kr,Fz in solution was obtained. Two low-temperature fluorination reactions of KrF, were also mentioned;8 iodine can be oxidized to
IF, and xenon to XeF,. The adduct KrF2,2SbF, is also an extraordinary
oxidizing agent. According to McKee et aL9 it will convert IF, into 1% and
XeOF, into XeOFz.
Elemental xenon can be oxidized by CI,Ft-Asq but not by ClF itself.1
The overall reaction is :
Thus the cation CI,Ff is a better oxidizing agent than CIF, just as XeF+ is a
better oxidizing agent than XeF,. The determination of the crystal structure
of XeF2,RuF, has been carried outll for the purpose of comparison with
that of XeF,,RuF5. The structure consists of discrete XeRuF, units in which
Xe is linearly co-ordinated to two fluorines (at 1.87 and at 2.18 A). The second
fluorine is also bonded to a distorted RuF, group; however, the ionic formulation XeWRuF; provides a simple and sufficient description of the structure.
A Raman spectroscopic study of a number of xenon@) compounds containing the XeFf cation has confirmed12 that v(Xe-F) is at approximately
610 cm-l. In addition there is a band at 340-380 cm-l in the AsF; and S b q
salts which is attributed to the Xe- * .F bridging stretch. Gillespie and Landa
concluded that the Raman spectra of XeF+M,F, (M = Sb, Nb, or Ta) contain bands attributable to this bridging stretching motion. Compounds containing the X e , q ion were also examined and up to seven of the expected
nine fundamentals were observed.
The successful gas chromatographic determination of XeF, on a column
filled with a porous polymer has been described.13The absorption spectra of
gaseous and solid XeF, measured in the 50-160eV region show the continuous contribution from the F and Xe components, and furthermore, a
R. L. DeKock, J . Chem. Phys., 1973, 58, 1267.
B. Frlec and J. H. Holloway, J.C.S. Chem. Comm., 1973, 370.
D . E. McKee, C. J. Adam, A. Zalkin, andN. Bartlett, J.C.S. Chem. Comm., 1973,26.
lo K. 0. Christe and R. D . Wilson, Znorg. Nuclear Chem. Letters, 1973, 9, 845.
l1 N. Bartlett, M. Gennis, D. D. Gibler, B. K. Morrell, and A. Zalkin, Inorg. Chem., 1973,
12, 1717.
l2 R. J. Gillespie and B. Landa, Inorg. Chem., 1973, 12, 1383.
l3 G. Gnauck and H. Schon, Z . Chem., 1973,13, 302.
678
detailed structure which could be deduced as being due to transitions from the
4d xenon core into the lowest empty valence and Rydberg states of the
molecules.14 The positions of the maxima are influenced by spin-orbit
splitting as well as by ligand-field splitting. Thus a core-level splitting caused
by the non-totally symmetric part of the ligand field has been reported for the
first time.
The most thermally stable compounds of the type Xe(OR), known so far
are Xe(OMF,), (M = Se or Te). Seppelt and Nothels have now reported
that the fusion of a mixture of the two compounds sets up the equilibrium:
Xe(OSeFJ2
+ Xe(OTeF,), + 2(F,SeO)Xe(OTeFs)
On the other hand, a study of the XeF,-XeF, system by d.t.a.and i.r.spectroscopy failed to detectle the formation of a stable addition compound nor any
evidence at temperatures up to 160 OC for the redox reaction to form XeF,.
The catalytic effect of HF on the fluorination of arenes by XeF, has been
discussed by Liebman and Vanderspurtl' in terms of its polarization of the
Xe-F bond. Such catalysis may be operating in the recently reported1*
benzoyloxylation of benzene. Treatment of benzene with benzoic acid and
XeF, in excess benzene leads to the reaction:
+ C6H6 + XeF2
C6HSCO2H
---+
CBH5C02C6Hb Xe
+ 2HF
with yields of phenyl benzoate of about 60%.

The use of XeF, as a mild and often selective fluorinating agent is becoming
increasingly common. The reaction with excess methyl iodide at room temperature produces methyliodine(Ir1) difluoride in quantitative yield.19 Under
more forcing conditions terbium(1v) fluoride can be prepared from TbF,.20
After one treatment with XeF, at 300-350C the product analysed as
TbF3.,: after a second treatment conversion into the +4 state was found to be
complete. It has also been reported that the oxidation of CrlI1 to CrV1can be
effected in weakly acid aqueous medium at 100C by XeF,.,l Microgram
quantities of chromium oxidized in this way were determined photometrically,
3 Xenon(rv)
Bartlett, McKee, and co-workers have investigated the XeF4-SbF5 system by

X-ray crystallographic and Ranian spectroscopic t e c h n i q u e ~ . ~They
l ~ ~ were
*~~
F. J. Comes, R. Haensel, U. Nielsen, and W. H. E. Schwarz, J. Chem. Phys., 1973,58,
516.
l6 K. Seppelt and D. Nothe, Znorg. Chem., 1973, 12,2727.
V. A. Legasov and A. S. Marinin, Russ.J. Znorg. Chem., 1973,18,298.
l7 J. F. Liebman and T. H. Vanderspurt, J. Fluorine Chem., 1973,2,413.
l 8 L. D. Shustov, T. N. Bocharova, T. 1. Yurasova, N. G. Marchenkova, V. A. Legasov,
and L. N. Nikolenko, J. Gen. Chem. (U.S.S.R.), 1973, 43, 841.
l9 J. A. Gibson and A. F. Janzen, J.C.S. Chem. Comm., 1973, 739.
2o V. 1. Spitsyn, Y. M. Kiselev, and L. I. Martynenko, Russ. J. Znorg. Chem., 1973, 18,
593.
21 A. Schneer-Erdey and K. Kozmutza, Acta Chim. Acad. Sci. Hung., 1973, 76, 179.
2 2 D. E. McKee, A. Zalkin, and N. Bartlett, Znorg. Chem., 1973, 12, 1713.
2 3 D. E. McKee, C. J. Adams, and N. Bartlett, Znorg. Chem., 1973, 12, 1722.
l4
The Noble Gases

679
able to isolate 1 :1 and 1 : 2 adducts but found no sign of 2: 1 adducts, which
might have contained the Xe,F: cation, The compounds are solids at room
temperature, and Raman spectra of the solids and of solutions in SbF, provided strong evidence for ionic formulations involving XeFz,23 thus confirming earlier 19Fn.m.r. spectroscopic
McKee, Zalkin, and Bartlett22
The T-shaped cation is
have determined the crystal structure of XeF:Sb,F,.
planar and lies in the same plane as a fourth fluorine, which is not bonded to
xenon (Xe- -F 2.50 A). There is thus a weak covalent interaction between
anion and cation which is also reflected in the lengthened bond between
antimony and the fourth fluorine. The geometry of the XeFl ion was compared with that of CIF:, and BrF,, both of which show larger F,EF,,
angles
and larger differences between E-Fa, and E-Feq bond lengths.
Semi-empirical MO calculations2son XeOF, have predicted that the CZv
molecule should have angle OXeF < 90". The absorption spectra of gaseous
and solid XeF, measured in the 50-160 eV region show similar features to
those in the XeF, spectra.14
4 Xenon(vx)
Ionization and total statistical energies of XeF, have been calculated26at the
experimental bond distance, assuming Oh molecular symmetry, using the
multiple-scatteringxu model. The ionization energies obtained in this way
are in better agreement with experiment than those from ab initio calculations.
The inability of XeF, to fluorinate XeFz at temperatures up to 160 "C has
been mentioned already.ls A new derivative of XeF, has been prepared,' by
the reaction with excess NOzF at 100 "C.The 1 :1 adduct, a colourless solid,
sublimes rapidly at 30 "C and was characterized by X-ray powder diffraction
patterns and molecular spectroscopy. The spectroscopicevidence and the total
dissociation in the gas phase are consistent with its formulation as a fluorinebridged adduct.
The crystal structure of XeFB,RuF, consists of discrete XeF, and RuF,
units, with each XeF, group co-ordinated to four RuF, via one fluorine atom
on each RuF,.ll The RuF, ions are less distorted in this adduct than in
XeF+RuF;. The co-ordination around xenon is thus nine-fold in a distorted,
capped Archimedian antiprism arrangement. The four longer Xe- - .F contacts
are symmetrically placed about the C, axis of the cation [Figure l(a)]. The
geometry of the XeF: ions in the 2XeF,,PdF4 structure is very similar2*
except that the co-ordination around each xenon is only 8, the three longer
Xe. * .F contacts being symmetrically placed about the principal axis of the
cation [Figure l(b)]. Another adduct 4XeF6,PdF, was also isolated and was
24
25
26
27
28
R. J. Gillespie, B. Landa, and G. J. Schrobilgen, Chem. Comm., 1971, 1543.

S.-C. Hsu, C.-Y. Ng, and W.-K. Li, J. Mol. Structure, 1973, 16, 125.
E. W. Phillips, J. W. D. Connolly, and S. B. Trickey, Chem. P h p . Letters, 1972, 17,
203.
J. H. Holloway, H. Selig, and U. El-Gad, J. Inorg. Nuclear Chem., 1973,353624.
K. Leary, D. H. Templeton, A. Zalkin, and N. Bartlett, Znorg. Chem., 1973, 12, 1726.
Figure 1 The XeFz structural units and their co-ordination in

XeFzRuF; and (b) [XeF~],[PdF~-]
(Reproduced by permission from Inorg. Chem., 1973,12, 1717, 1726)
680
The Noble Gases

681
shown by Raman spectroscopy to contain the Xe,F,f, ion. The crystal structure
of the adduct 2XeF6,AuF, has shown29that the cation in this novel hexafluoroaurate(v) compound can be described as two XeFQ ions linked by F [Figure
2(a)]. The co-ordination number of xenon is seven in this compound and yet
the weaker Xe * *F interactions are again found in the region of space
between the lone pair and the four equatorial fiuorines [Figure 2(b)].
Figure 2 (a) The structural unit of [X!&,[+[AuF,]-.

(b) A representation of
the influence of Xe non-bonding valence-electron pairs upon the
polarizing character of the XeFz ion (arrows indicate directions of
maximum polarization of anions)
(Reproduced from J.C.S. Chem. Comm., 1973, 131 and by permission from
Inorg. Chem., 1973,12, 1726)
19Fn.m.r. relaxation-time measurements on XeOF, have been made30in the
temperature range -56 to +85 "C.The results were found to be indicative of
associative interactions in the liquid state. The vl, Xe===Ostretching motion,
Raman band of liquid XeOF, samples is patently asymmetric, although this
fact has not been commented on earlier. Waldman and Selig31 have now
reported that this band is also asymmetric in solutions of XeOF4 in liquid
HF and moreover that it consists of two components whose intensities vary
with the XeOF, concentration. These workers compare this phenomenon to
the variation in the shape of v1 for IF,, attributing it to weak associative
interactions between XeOF, (or IF,) molecules.
Further studies of the reactions of XeOF4 with the Lewis acids AsF, and
SbF, have rsvealed two new adducts, viz. 2XeOF4,AsF,, which dissociates
29
31
K. Leary, A. Zalkin, and N. Bartlett, J.C.S. Chem. Comm., 1973, 131.

J. C. Hindman, J. G. Malm, A. Svirmickas, and H. D. Frame, J. Mugn. Resonance,
1973,9,428.
M. C. Waldman and H. Selig, J. Inorg. Nuclear Chem., 1973, 35, 2173.

above -25 O C , 3 l and XeOF4,SbF5.9~23031
The new antimony complex is ionic
and, like the previously reported XeOF4,2SbF, adduct , contains the XeOFi
ion, according to Raman spectra of the solid.
Semi-empirical MO calculations have been carried out on XeOF, and
Xe02F2.25The predicted bond angles in the C,,molecule were OXeO < 120'
(observed3, 105.7') and OXeF < 90" (observed3, 91.6'). Peterson et a1.3, have
determined the molecular symmetry and structure of Xe02F2from singlecrystal neutron-diffraction data. The results are in general agreement with the
682
Figure 3 Part of the layer structure of XeO,F,, the angle X-0.

-Xe being
168.5'. There are no close contacts between parallel layers
(Reproduced by permission from J. Chem. Phys., 1973, 59,453)
earlier i.r. and Raman study and show that the molecular structure is based
upon a trigonal bipyramid with fluorines occupying the axial positions. The
20 cm-l shift of the antisymmetric Xe===Ostretch in going from the liquid to
.Xe bridges
the solid state may be attributed to the presence of weak X-0.
in the solid (Figure 3). A surprising feature of the structure is that angle
OXeO < 120' whereas FXeO > 90'.
The effects of pH and 7-ray intensity on the radiolysis of aqueous solutions
of Xe03 have been in~estigated.3~
The existence of XeOz was proposed as an
intermediate in this decomposition reaction as well as in the thermal reaction
of Xe03 with hydrogen peroxide. A novel reaction of Xe03, organic m-bond
epoxidation, has been described.MAqueous XeO, has been shown to react
with certain olefins, yielding the corresponding epoxide as the major product.
Xenate(v1) ion was proposed as the major epoxidizing species, although the
32
34
S. W. Peterson, R. D. Willett, and J. L. Huston, J. Chem. Phys., 1973,59,453.

M. Haissinsky and C. Heitz, J. Chim. phys., 1973, 70, 733.
S. A. Shackelford and G. U. Yuen, Inorg. Nuclear Chem. Letters, 1973,9,605.
The Noble Gases

683
perxenate ion cannot be excluded since a small steady-state concentration of
perxenate could be present from xenate disproportionation.
5 Xenon(vrr1)
McKee, Adams, Zalkin, and Bartletts have now carried out the oxidation of
XeOF, to XeOFz by means of the reaction:
XeOF,
"C
+ KrF+Sb2FG -10
>
-
XeOFtSb2Fil
+ Kr
Since the syntheses were performed in quartz apparatus, 0; salts were always
found as contaminants. Raman-spectroscopic data for the new cation were
consistent with an IOF,-like species.
Author Index
Aarons, L. J., 469

Abbasov, B. S., 79,
Abbasov, M. A., 18,
Abdel-Rehim, H. A.,
548
Abdullaev, G., 78,
Abdullaev, G. K.,
79, 87, 157
Abdullaev, G. V., 619
Abdullaev, M. Yu., 648
Abdullina, N. G., 608
Abe, T., 591, 618
Abel, E. W., 372, 389
Abisheva, Z., 16,
Abouaf-Marguin, L.,
266
Abrahams, S. C., 203
Abrham, K., 175
Abrikosov, H. K., 623
Absar, I., 481
Abykeev, K., 18
Achard, J.-C., 425, 427
Acharya, P. K., 632
Acharya, T. R., 233
Achatz, M., 242, 297
Ackerman, J. P., 50
Ackermann, M. N., 444
Adachi, G., 554
Adamovich, L. P., 59
Adams, C. J., 549, 592,
621,661,677, 678
Adams, D. A., 505
Adams, G. F., 450
Adcock, J. L., 148, 162
Addison, C. C., 5,457
Addison, K. S., 505
Adlkofer, J., 357,
Adorian, I., 66
Adrian, F. J., 36, 617
Aerny, J., 100
Afanasiadi, L. I., 61
Afinogenov, Yu. P.,
213,224
Afzal, M., 41
Agafonov, I. L., 521
Agarkov, G. A., 408

Agarwal, M. M., 185
Agarwal, M. P., 3 12
Agrinier, H., 542
Agureeva, L. K., 197
Ahl, J. L., 669
Ahlrichs, R., 73, 111
Ahluwalia, S. C., 357
Ahmad, D., 56,631
Ahmed, A. H. M., 96,
188
Ahmed, F. R., 505
Ahmed, S., 519
Ahnell, J. E., 650
Ahrens, U., 486
Ahumada, J. J., 267
Ainscough, A. N., 230
Ainsworth, R. G., 611
Aizawa, M., 570
Akada, W.,362
Akatsuka, K., 207
Akbaev, A., 18
Akhmetov, S. F., 632
Akhmetova, F. V., 533
Akhmetova, G. L., 632
Akhmadeev, V. Ya., 537
Akhmedi, M. K., 208
Akimov, V. M., 215
Akishin, P. A., 69
Akitt, J. W., 82, 185,
570,571
Akiyama, N., 236
Akiyama, T., 381, 522
Akopov, E. K., 222, 613
Aksela, S., 614
Aksens, D. W., 539, 543
Akulov, A. N., 351
Alakhanyan, A. G., 18
Alange, G. G., 601
Albert, S., 440
Alberti, G., 521
Albrand, J. P., 470
Alcock, N. W., 49, 276,
610
Alcock, W. G., 245
684
Alduin, F. A., 104

Alecu, I. D., 201
Alei, M., jun., 438
Aleksandrov, A. Yu., 545
Alekseeva, I. I., 662
Alekseeva, T. E., 224
Aleksic, B. D., 434
Aleonard, S., 74
Aleskovskii, V. B., 321
Alexakos, L. G., 659
Alexander, L. E., 308,
547,640
Alexandrov, A., 2 16
Alfassi, Z. B., 250
Alford, K. J., 180
Alikhanyan, A. S., 40
Alimarin, I. P., 458
Alkemade, C. Th. J.,
89
Allan, C. J., 104, 271,
578
Allakhverdov, G. R., 642
Allario, F.,454
AIlcock, H. R., 507, 512,
517
Allen, A. D., 431
Allen, C. W., 371
Allison, D. A., 104, 271,
578
Allison, J., 104
Allsalu, M., 89, 578
Allulli, S., 521
Almenningen , A., 168,
176, 180,605
Almlof, J., 571, 668
Alpatova, N. M., 498
Alric, A.-M., 493
Al-Shenavi, H. M., 158
Alshin, B. I., 354
Al-Siddiqui, F. R., 631
Althoff, W., 488
Aly, M. M., 186
Alyamovskaya, K. V.,
335,338
Alyamovskii, S. I., 11, 236
Author Index
Alyea, E. C., 375
Amamoto, T. Y., 243
Amano, T., 665 4
Amarii, V. Z., 219
Amaro, A. A., 189, 341
Amaudrut, J., 455
Amberg, C. H., 589
Amcrasit, M., 194
Ames, L. L., 79, 235
Amiel, S., 250
Aminadav, N., 490
Amita, K., 279
Amma, E. A., 307
Amosov, A. V., 317
Anagnostopulos, M. L.,
144
Ancy-Moret, M. F., 52,
79,575
Andermann, G., 573
Andersen, A. F., 468,
532
Anderson, A., 272, 466
Anderson, D. W. W.,
398,449,490,494
Anderson, G. A., 162,
176
Anderson, G. R., 671
Anderson, J., 405
Anderson, J. G., 463
Anderson, J. W., 291,
372, 382, 532
Anderson, R. A., 76
Anderson, T. N., 274
Anderson, S., 547, 644
Ando, Y., 297
Andrae, H. J., 1
Andra, K., 539
Andreev, I. F., 93, 111,
327, 336, 365, 523
Andreevichev, V. S., 401
Andrews, L., 35, 37, 38,
48, 51, 250,451,453,
561, 563, 564,652
Andrianov, K. A., 297,
298, 302, 355
Andronova, N. P., 18
Andrushchenko, N. S.,
155
Anfimova, T. M., 254
Ang, H. G., 534
Angadi, R. P., 529
Angell, C. L., 189, 345,
346
Angus, P. C., 290
Anlauf, K. G., 669
Anisimov, K. N., 394
Anisimova, E. A., 61
Anisimova, V. N., 632
Annabi, F., 351
Anno, T., 565
Annopol'skii, V. F., 184,
191, 280
685
Anokhina, A. A., 213
Ansari, S., 382,480, 534
Anthoney, M. E., 196
Antipov, I. N., 649
Antonelli, L., 655
Antonini, M., 648
Antonova, L. I., 628
Antoshina, 0. M., 59
Anugul, S.,468
Aoyagi, T., 186
Apelblat, A., 617
Appel, R., 144,377, 378,
512, 597
Appelman, E. H., 665,
667
Apraksin, I. A., 181
Araki, S., 199, 372
Araki, T., 87, 156, 186
Aravamudan, G., 644,647
Archie, W. C., jun., 517
Ardon, M., 457, 668
Arick, R. M., 25
Ariguib-Kbir, N., 542
Aritomi, M., 364
Arkhanoel'skii, I. V., 346
Arkhipov, S. M., 18, 194,
195
Arkhipova, N. F., 224
Armstrong, D. A., 464
Armstrong, D. R., 114,
161,658
Armstrong, J. A., 273
Armstrong, R. S., 142
Arnau, J. L., 564
Arnold, D. E. J., 292,
489
Arnold, G. P., 237
Arnold, S. J., 266
Arnol'dov, M. N., 6
Aronson, S., 13,224
Arrowsmith, A., 435
Artem'ev, V. P., 281,
613
Arthur, N. L., 294, 614
Aruldhas, G., 473
Asadov, Yu. G., 459
Asbrink, L., 287
Ashavskaya, G. A., 298
Ashby, E. C., 46, 175
Ashe, A. J., tert., 556
Ashford, N. A., 454
Aslamya, D. G., 184
Aslanov, L. A., 515
Aslanyan, D. G., 617
Asmus, K.-D., 446
ASSO,L., 154
Asso, M., 154
Astrom, A., 547, 644
Asworth, J. R., 338
Atabaeva, E. Ya., 559,
628
Atchayya, M., 196
Atkinson, I. B., 161

Atkinson, R., 453, 562
Atkinson, S. J., 270
Atoda, T., 547
Atovmyan, L. A., 361
Atovmyan, L. O., 189
Atwood, J. L., 177, 179
Avinens, C., 490
Aubke, F., 365, 366,
614, 661,663
Aubry, J., 47, 88,444
Audinos, R., 456
Aulakh, G. S., 536
Aulich, H., 20
Ault, B. S., 436, 671
Aurivillius, K., 44
Autera, J., 450
Autzen, H., 374
Averbach, B. L., 545,
619, 627
Averbuch-Pouchot, A. T.,
522
Averbuch-Pouchot,
M.-T., 524,526, 527
Avilov, A. S., 223
Axenrod, T., 450
Axworthy, A. E., 651
Ayasse, C., 326
Aylett, B. J., 301, 302,
314,450
Aymonino, P. J., 664
Ayscough, P. B., 363
Azarova, L. A., 18, 667
Azimov, Sh. Yu., 93,
327, 365, 523
Azizova, B. B., 623
AZOU,P., 174
Azzopardi, M., 409
Baalmann, H. H., 513
Babaev, B. K., 625
Babaeva, E. P., 524
Babaeva, V. P., 57, 154
Babenko, A. M., 18,461
Babitsyna, A. A., 216
Bacci, M., 673
Bach, M.-C., 142,481
Bacha, A., 427
Bach-Chevaldonnet ,
M.-C., 145
Back, M. H., 449
Bacon, J., 659
Bacon, M., 220,562
Baddour, R. F., 238
Baenziger, N. C., 309,
381
Baer, M., 250
Baer, T., 246
Baerlocher, C., 189
Baes, C. F., jun., 149,
301
Bagieu, M., 528
Author Index
686
Bagieu-Beucher, M., 528
Bagirov, S. B., 619
Bagus, P. S., 676
Baidakov, L. A., 531
Bailey, P. L., 284, 615
Bailey, W. C., 209
Baird, N. C., 160, 260,
444
Baird, T., 267
Baise, A. I., 247, 248
Bajpai, K. K., 383
Bakalov, V. D., 614
Bakeev, M. I., 632
Bakeeva, S. S., 632
Baker, A. D., 39
Balasubrahmanyam, K.,
63,220,459
Baldanov, M. M., 100
Baldwin, J. C., 424
Baldwin, R. R., 452
Balej, J., 19, 613
Balicheva, T. G., 553,
667
Ball, M. C., 520, 611
Ball, R. D., 396, 397
Bamberger, C. E., 301
Bancroft, G. M., 307,
392, 394,397
Bandoli, G., 399
Bandy, A., 618
Banerji, S. K., 187
Banister, A. J., 600, 601
Barabas, A., 77, 154
Barabash, A. I., 613
Barabash, Yu. V., 524
Baran, E. J., 664
Baranovskii, I. B., 205
Barassin, J., 251
Barat, F., 666
Barber, M., 143, 233
Barcza, L., 657
Bardi, G., 10, 546
Bar-Eli, K., 21
Barili, P. L., 655
Barker, B. J., 656
Barker, G. K., 291, 372
Barker, M. G., 7
Barkova, F. F., 328
Barnaud, J. D., 207
Barnert, D., 574
Barnes, A. J., 249, 672
Barnum, D. W., 360
Baron, B., 20
Barrau, J., 418
Barrer, R. M., 189, 340,
341
Barrette, L., 650
Barrick, J. C., 597
Barrow, R. F., 573
Bartell, L. S., 482, 676
Barthel, C., 634
Barthelat, J. C., 242
Barthomeuf, D., 346

Bartlett, N., 549, 592,
613, 661, 677, 678,
679, 681
Barton, L., 167
Baryshnikov, Yu. M., 87
Baryshok, V. P., 361
Bascom, W. D., 319
Bashkirov, S. A., 403
Basile, F., 353
Basov, V. P., 550
Bassett, P. J., 80
Bassi, G., 525, 527, 528
Bastian, E. J., 579
Bastick, J., 184
Bastow, T. J., 543, 545,
627
Batca-Cerbu, A., 59
Bates, J. B., 36, 65,265,
317
Bates, R. D., 504, 591
Batsanov, S. S.,289
Batsanova, L. R., 72
Batts, B. D., 225
Batyaev, E. A., 293
Bau, R., 137
Baudler, M., 469, 470,
475, 529, 532
Baudot, V., 17
Bauer, G., 290,291
Bauer, H. F., 659
Bauer, S. H., 119, 594,
665
BauBr, Ya., 340
Baughman, R. J., 425
Baumgartner, E., 48
Baur, W. H., 329, 336,
524
Baverez, M., 184
Bayer, E., 21
Bayer, G., 333
Bazant, V., 297
Bazhanov, A. P., 351
Beachley, 0. T., jun.,
163, 180
Beagley, B., 525, 555
Beattie, I. R., 308, 547,
640
Beaty, R. D., 636
Beaudet, R. A., 151
Beaudet, R. G., 141
Beaumont, R. E., 555
Becart, M., 192
Becher, H. J., 73, 173,
278, 629
Becke-Goehring, M.,
496,604
Becker, F., 356
Becker, W., 176, 635
Beckstead, L. W., 427,
429
Beckurts, K. H., 560
Beckwith, A. L. J., 516

Bedwell, V. E., 659
Beech, T. A., 541
Beer, D. C., 120, 131, 135,
42 1
Beer, G., 165
Beer, H., 492
Beer, J. M., 435
Beers, Y., 260
Begun, G. M., 546
Behar, D., 283
Beierl, D., 550
Beilen, Yu. A., 416
Bekkerman, L. I., 192
Belichenko, V. P., 575
Belin, C., 669
Bell, B., 601
Bell, N. A., 73
Bell, S., 265
Bellamy, L. J., 569
Belokoneva, E. L., 326,
350,351,352
Belonogova, L. N., 79,
351
Belotskii, D. P., 212,
623
Belous, G. F., 529
Belousova, E. M.,315
Belov, N. V., 87, 326,
327, 329, 336, 350,
351, 352, 583, 608
Bel'tyukova, S. V., 100
Belyaev, E. K., 184, 280
Belyaev, I. N., 408
Belyaev, L. M., 352
Bendazzoli, G. L., 245,
255
Bender, C. F., 257
Benedict, J., 486
Benesovsky, F., 171, 173,
237
Bennett, W. E., 381
Benno, R. H., 371, 579
Bensted, J., 325
Ben Taarit, Y.,346
Bentham, J. E., 494
Benton-Jones, B., 141
Bentrude, W. G., 516
Ben'yash, E. Ya., 276,
422
Berak, J., 526
Berdnikov, V. R., 192,
5 07
Berend, G. C., 669
Berentsveig, V. V., 346
Berenzhanov, B. A., 613
Bereslovtseva, L. F., 212
Beretka, J., 280
Berezhinskii, L. I., 582
Berezina, M. I., 76, 621,
632
Berezkin, V. V., 351
Author Index
Berger, A. S.,44,202,
279, 328, 339
Berger, H., 243
Berger, L. I., 626
Berger, M., 283
Berger, R. L., 335
Berger, W., 484,641
Bergerhoff, G., 406
Bergesen, K., 514
Bergman, A. G., 18, 352,
46 1
Berkley, R. E., 294
Berkowitz, J., 213, 223,
664,665
Berlin, B., 36
Berlow, P. P., 246
Bermann, M., 495, 509,
514
Bermark, T., 436
Bermudez, V. M., 628
Bernander, L., 550
Bernard, J. P., 589
Bernardi, F., 255
Berney, C. V., 466
Bernstein, E. R., 112,
162, 287
Bernstein, J. D., 180
Bernstein, J. L., 203
Bernstein, P. A., 259
Bernstein, R. B., 250
Berry, A. D., 314
Berry, H. G., 1
Berry, M. J., 261
Bertenev, V. M., 271,
579, 606
Berthet, G., 519
Berthier, G., 438
Bertie, J. E., 671
Bertrand, G. L., 98
Bertraut, E. F., 519
Berul, S. I., 49, 554,
585, 587, 628
Bes, R., 452
Beskrovnaya, R. A., 370
Bessard, J., 666
Besson, J., 409
Bessonov, A. F., 202
Best, D. F., 346
Betrencourt, M., 246
Betrencourt-Stirnemann,
C., 246
Bett, J., 234
Bevan, P. L. T., 563
Bever, M.B., 425
Bezrukova, E. A., 155
Bhalla, S. K., 315
Bhasin, S. K., 77
Bhat, N. V., 656
Bhatia, J. C., 518
Bhattacharya, P. K., 77
Bhattacharya, S. N., 383
Bhaumik, B. B., 19
687
Bianchin, B., 442
Bichon, J., 21
Bienenstock, A., 626
Bigvava, A. D., 649
Billaud, D., 239
Billy, M., 355, 379
Bilton, M. S., 328
Binder, H., 529, 530, 592
Binder, P. E., 268
Binnewies, M., 195, 214,
308
Biradar, N. S., 312, 315
Birchall, T. , 352, 547,
553
Bird, S. R. A., 392,407
Birk, J. P., 668
Birke, P., 526
Birnbaum, G., 435
Birss, F. W., 260
Biryulina, V. N., 476
Bischof, J. , 59
Bisell, E. C., 507, 517
Bishimbaev, V. K., 19
Bishop, E., 284,615
Bishop, R. J., 346
Bither, T. A,, 156, 158
Bitner, J. L., 233
Bitter, W., 377, 495
Bittner, H., 352
Bizot, D., 223
Bjerrum, N. J., 195, 640
Bjorkholm, P., 649
Bjorply, M., 514
Blachnik, R., 628
Black, G., 464
Blackborow, J. R., 143
Blackman, G. L., 449
Blackwell, L. J., 456,
457
Blackwood, J. D., 235,
607
Blagoveshchenskaya, G.
I., 621
Blair, L. K., 656
Blanchard, C., 475
Blank, A. B., 61
Blank, G., 84
Blasius, E., 100, 531, 618,
633, 635
Blasse, G., 558
Bleidelis, Ya. Ya., 361
Bleshinskii, S. V., 36
Blint, R. J., 104
Bliznakov, G., 171
Blomfield, G. A., 320
Bloom, H., 407
Bludova, L. N., 52
Blue, J. W., 650
Bluke, R., 176
Blum, F. A., 454
Blumenberg, B., 440
Blundell, D. C., 161
Blyholder, G., 270, 566

Boal, D., 315
Bobin, B., 243
Bocharova, T. N., 678
Bochkarev, M. N., 370,
401,402
Bock, H., 261, 591
Bock, M., 475
Bock, R., 657
Bocquet, J.-F., 17, 460
Bocquillon, C., 327
Boczkowski, R. J., 307
Bodak, 0. I., 427
Boden, P., 187
Bodner, G. M., 106, 116
Boeck, A., 241
Boenig, I. A., 142, 150,
503
Boese, R., 393
Boesenberg, J., 1
Boti, Z., 217
Bogacheva, L. M., 189
Bogdanov, V. S., 149
Bogdanova, A. V., 587
Boguslawska, K., 59
Boggs, J. E., 256, 453
Bogoyavlenskii, P. S.,281
289
Bohac, P., 554,628
Bohme, D. K., 434, 657
Boivan, J.-C., 558
Bokii, G. B., 609
Bokii, N. G., 304
Boller, H., 236,468,469,
559, 628
Bolshutkin, D. N., 249
Bolter, H., 532
Bolton, K., 449
Bombieri, G., 276
Bond, A., 144
Bond, A. C., 113
Bondar, I. A., 336
Bondarenko, N. V., 66
Bondybey, V. E., 444
Bone, L. I., 589
Bonelli, D., 377
Bonn, M. G., 325
Bonneau, R., 652
Bonner, F. T., 452
Bonnetain, L.,280, 607
Bonnetot, R., 176
Bonzel, H. P., 270
Boo, W. 0. J., 103
Boolchand, P., 649
Bopp, T. T., 598
Borchner, J., 21 1
Bordes, E., 527
Bordner, J., 555
Borel, M. M., 34, 92
Borgstedt, H. U., 7, 8,
560
Borisov, S. N., 356
688
Borisova, V. V., 390
Borisova, Z. U., 587
Borjakova, V. A., 212,
625
Borkett, S.,421
Borntnikova, T. P., 613
Borodko, Yu. G., 431
Borovaya, V. A., 19
Borovinskii, L. A., 4
Bos, A., 352, 561
BOS, K. D., 413
Bosch, R., 573
Boschman, F. E. H., 363
Bosio, L., 199
Bosworth, Y. M., 466
Bott, J. F., 669
Bottari, E., 422
Bottei, R. S., 307
Bouaziz, R., 155
Boucekkine, A., 161
Bouchard, R. J., 353, 553
Boucher, C., 329
Boudjouk, P., 384
Bouel, G., 523
Bouix, J., 170, 590
Bousquet, J., 55, 578
Bousquet, J. L., 268
Bowman, A. L., 237
Bowers, V. A., 36, 617
Boyd, A. W., 268
Boyd, D. B., 575
Boyd, G. E., 36, 65, 461,
566
Bozhevolnov, E. A., 101
Bozzelli, J. W., 250, 651
Bradaczek, H., 602, 606
Bradley, D. C., 375
Bradley, E. B., 150, 388,
503
Bradley, J. N., 455, 580
Braeutigam, G., 65
Braithwaite, J., 427, 429
Bramlet, H. L., 276
Brand, J. C. D., 456,
607
Brandt, G., 193
Brandwijk, V., 42
Bratton, R. F., 167
Brattsev, V. A., 131
Brauer, G., 94, 545
Brault, J.-F., 514
Braun, A. B., 249
Braun, R. W., 483
Braunstein, H., 64
Braunstein, J., 64
BrEiE, B. S., 557
Brec, R., 179
Breckenridge, W. H., 560
Breda, A. C., 656,676
Breda, F., 438, 671
Bredig, M. A., 459, 555
Breeze, A., 318, 658
Author Index
Breick, V., 176
Bremer, H., 184, 324
Bremner, R. O., 49
Brennan, J. P., 107
Bretschneider, E. S., 371
Brezeanu, M., 398
Brezgin, Yu. A., 213
Brezhneva, N. E., 102
Brice, J. F., 47, 88, 444
Brice, M. D., 421
Brice, V. T., 106, 107,
114
Bridgart, G. J., 439
Bridges, L., 258
Briggs, A. G., 151
Briles, G. H., 546
Brill, T. B., 308, 482,
540,642
Brisse, F., 553
Broadhead, P., 152, 571
Broberg, D. E., 381
Brodersen, K., 218
Brodin, I. I., 427, 648
Brom, J. M., jun., 81,
170, 171,237, 578
Bronger, W., 588
Brooker, M. H., 36,
459,461
Brookes, A., 395
Brookes, M. H., 566
Brooks, D. L., 500
Brooks, J. J., 31
Bros, J. P., 12
Brossard, M., 379
Brotchie, D. A., 147, 464
Broudy, P. M., 314
Brough, B. J., 64
Brouwer, D. M., 549
Brower, W. S., 212
Brown, C., 120
Brown, C. L., 121
Brown, C. W., 562,611
Brown, D. H., 195
Brown, H. C., 160
Brown, I. D., 44, 308,
609
Brown, J. D., 485
Brown, K. L., 205
Brown, L. L., 225
Brown, M. E., 413
Brown, M. P., 131
Brown, 0.R., 438
Brown, R. D., 449,464
Brown, R. J. C., 556
Brown, W. E., 5 5 , 542
Brownstein, M., 622
Bruile, E. S., 18
Bruinink, J., 671
Brun, B., 23
Brun, G., 475, 476, 515,
612, 613
Brundle, C. R., 39, 270
Bruniquel, M.-F., 497,

506
Brunisholz, G., 100
Bruns, R. E., 260,261
Brunner, A., 58
Bruno, P., 23
Brupbacher, J. M.,282
Bryukhova, E. V., 542
Bryuchova, E. V., 314
Buchner, W., 479,489
Buck, P., 204,531, 578,
587
Buck, R. H., 409
Buckle, J., 313
Budarina, A. N., 68
Budding, H. A., 413
Budenz, R., 591
Buder, W., 550
Buchler, A., 204, 220
Buenker, R. J., 434, 439
Biinzli, J. C., 492
Burger, H., 51,425, 472,
474,533, 534
Buerger, M. J., 156
Bugg, C. E., 89,91,92
Buiten, J., 423
Bujewski, A., 643
Bukakhova, V. I., 276
Buketov, E. A., 53, 584
Bukhalova, G. A., 336,
352, 524
Bukovec, P., 194
Bula, M. J., 170
Bulanova, G. G., 44
Bullen, G. J., 140, 164,
472,497, 504, 511
Bulliner, P. A., 613
Bullock, G. E., 283
Bullock, J. I., 485
Bullock, R. E., 230
Bulo, V. S., 78,427
Bulten, E. J., 413
Bulusu, S., 450
Bundy, F. P., 227
Bunyatyan, B. Kh., 14
Buraya, I. T., 520
Burden, F. R., 449,464
Burdge, J. J., 444
Burg, A. B., 122, 141,
473
Burgard, M., 550
Burger, K., 15, 306
Burley, B. J., 337
Burnelle, L. A., 148, 284
Burnham, R. A., 392
Burrows, B., 63
Buryakov, A. V., 224
Buschow, K. H. J., 172,
207
Busev, A. I., 199
Buslaev, Yu. A,, 303, 656
Busman, S. C., 450
Author Index
Buss, B., 484, 513, 641
Busse, P. J., 167, 388
Butenko, G. A., 101
Butherus, A. D., 238
Butikova, I. K.,325, 331
Butler, K. D., 307, 392,
397
Butler, W. M., 169
Butman, L.A., 192, 507
Buttery, H., 392
Buttner, H.-J., 644
Butuzov, V. I., 227
Butwill-Bell, M. E., 567
Buxton, G. V., 263
Buxton, T.L., 24
Buyakov, A. A., 299
Buzagh-Gere, E., 81
BuzeSanu, M. G., 244
Bychkov, V. T., 399
Byerley, J. J., 413, 579
Bykova, M. A., 12, 13
Byler, D. M., 550
Bytyrchaev, I. E., 18
Cabana, A,, 159, 243,
266, 272
Cachau-Herreillat, D. ,
49, 638
Cachiolo, B., 148
Cadene, M., 34
Cadogan, 3.1. G., 539
Cadot, J., 243
Cady, G.H., 261,540,
558, 595,623, 654, 663
Cafasso, F. A., 2
Cairns, E. J., 2, 3, 576,
624,648
Calabrese J. C., 114
Calcaterra, M., 517
Calderazzo, F., 32,440
Calhoun, H. R., 474
Callahan, K. P., 138, 139
Calleri, M., 535
Calligaris, M., 369
Calvo, C., 52, 410,477,
519, 524,527, 542
Cambell, I. D., 543
Campanella, L., 422
Campbell, A. N., 207
Campbell, N. C., 540
Cameron, T. S., 502, 530
Cameron, W. E., 338
Canet, D., 185
Cannillo, E., 329
Cannon, R. E., 177
Capdevila, C., 104
Capponi, J. J., 156
Caranoni, C., 221
Carbato, L., 207
Carbonneau, R., 431
Carcaly, C., 370, 626
Cardona, M., 78, 620
689
Cardini, L., 108
Carlson, T. A., 39, 83,
245,271, 307, 579
Carlstrom, D., 355
Carmona, F., 229
Carpenter, R. A., 569
Carpentier, C. D., 204,
531, 587
Carponi, G., 154
Carraher, C.E., 359
Carreira, L. A., 145,
265, 470
Carrell, H. L.,33, 671
Carrington, T., 453
Carroll, T. X., 482, 591,
658
Cgrsky, P., 257

Carter, H. A., 593, 618
Carter, J. C., 109
Carter, R.O., 265, 383
Carton, B., 239
Carty, A. J., 203
Carver, J. G., 83
*so,
J. A,, 24, 656
Cgsenskf, B., 175, 17
Casey, M., 228
Casson, M. J., 520
Castagnolo, M., 16
Castan, P., 493
Castanet, R., 224, 648
Castellano, E., 655
Castellonkse, P.,662
Castro, E. A., 152
Catlett, D. S., 45
Catrett, F. D., 403
Catti, M., 542
Caucanas-Dumail, M.,
515
Cauquis, G.,666
Cavell, R. G., 485, 489,
493
Cazzoli, G., 255
Cecal, A., 217, 218
Cederbaum, L. S., 430
Cenini, S., 392
Centofanti, L. F., 145,
481,485, 501
Ceraso, J. M., 28
Cerchez, M., 341
Cerovic, D., 236, 468
Cescon, P., 574
Cessac, G. L., 618
Chabrier, P., 514
Chachaty, C., 562
Chachava, G.-N., 535
Chackraburtty, D. M.,
222
Chadaeva, N. A., 543
Chadwick, D., 595
Chahvekilian, E., 9
Chaigneau, M., 657
Chakladar, J. K., 516

Chamberland, B. L., 212
Chaminade, F., 5
Champarnaud-Mesjard,
J. C., 43
Champion, J. P., 243
Chan, C. H., 195, 601
Chan, F. T., 664
Chan, S., 372
Chan, S. O., 306
Chandraiah, G., 454
Chang, C.-A., 81, 198
Chang, H. C., 561
Chang, H. W., 250
Chantret, F., 542
Chao, C.-C., 344
Chapados, C., 243
Chapuis, G., 212, 559,
585
Chapyzhnikov, B. A., 3
Charlesworth, G., 179
Charlot, J. P., 48
Charov, A. I., 370
Charvillat, J. P., 533
Chasanov, M. G., 35
Chassang, J., 223
Chastagnier, M., 657
Chatelain, A., 326
Chatillon, C., 198
Chatillon-Colinet, C.,
427
Chatterjee, A. K., 516
Chatterji, D., 201
Chaturvedi, C. V., 289
Chaturvedi, V. S., 210
Chaudhri, S. A., 446
Chaudry, N. P., 41
Chauhan, R. K., 285
Chaus, I. S., 554, 585
Chawla, 0. P., 614
Che, M., 324, 566
Chebotarev, N. T., 611
Chekhun, A. L.,515
Chemla, M., 16, 17,
460
Chen, G. S. H., 483
Chen, I., 620
Chen, K. Y.,589
Chen, M. M., 296, 491
Chen, M. T., 151, 641
Chen, S., 281
Chenavas, J., 156
Cheng, H. S., 311
Cheng, K. L., 83
Cheng, T. M. H., 296
Cherepennikova, N. F.,
40 1
Chernaya, N. V., 202
Cherneeva, L. I., 10
Chernokalskii, B. D.,
535, 536, 537
Chernoplekova, V. A., 304
690
Chernov, A. P.,542
Chernov, D. B., 426
Chernova, A. D., 357
Chernozubov, Yu. S.,
619
Chernyavskaya, E. I.,
522
Chernyavskii, L. I., 271

Chernyavskii, L. N., 579
Chernyshev, E. A., 403
Chernyshov, B. N., 149
Chervinskii, Yu. F., 71
Chevaleyre, J., 590, 654
Chevrier, B.,551
Cheyne, B. M., 636
Chezeau, N., 370,626
Chiang, Y., 670
Chichagov, Yu. V.,240
Chicharova, A. D., 183
Chickerur, N. S., 365
Chihara, H., 483
Chikanov, N.D., 547,
551,557
Chikov, V. S.,89
Ching, C., 261
Chiu, Y.-N.,
453
Chivenkov, A. N., 192,
520
Chivers, T., 589

Chizhevskaya, S. N., 623
Chizhikov, D. M., 350,
557
Cho, C. W., 454

Choi, J. S.,268
Cholokov, K. S.,40
Chong, T., 299
Choo, K. Y.,296
Choudhari, B. P., 278
Chouteau, J., 371
Chowdhry, V., 128
Chretien, A., 71
Christe, K. O., 538, 594,
651, 658, 659, 660,
664,677
Christian, G. D., 422
Christoffersen, R. E.,
43 3
Christophliemk, P., 151
Chuang, T. T., 274,607
Chuchalin, L. K., 219
Chudinova, N. N., 521
Chugunov, V. D., 43
Chuiko, A. A., 318, 321
Chuiko, V. T., 518
Chukhlantsev, V. G.,
335, 336
Chukova, V. M., 509

Chukurov, P. M., 76
Chulkova, L. V., 253
Chung, C., 595
Chung, S. J., 74
Chuong, T.-K., 324
Author Index
Chupka, W. A., 664
Churaev, N. V., 569
Churchill, M. R., 128,
137, 433
Chutonov, K. A., 11
Chuvaev, V. F., 515
Ciach, S., 406
Cichon, J., 472,474, 533,
534
CinnBide, S. 6 ,
536
Ciurylo, I., 13
Ckianova, M. K., 303
Claire, Y., 224, 648
Clapp, C. H., 479
Clapp, D. B., 161
Clardy, J. C., 498
Clare, P., 505
Clark, C. D., 228
Clark, D. B., 651
Clark, H. C., 392
Clark, J. R., 158
Clark, N. J., 237
Clark, R. J. H., 247, 306,
466
Clarke, J. H. R., 60
Clarke, R. M., 244
Claudy, P., 176
Claus, R.,317
Clausing, R. E., 1
Clayton, W. R., 126
Claxton, K. T., 8
Clearfield, A., 521
Clemente, D. A., 399
Clementz, D. M., 332
Clough, P. N., 273
Clouse, A. O., 106
Cloyd, J. C., jun., 473
Clyne, M. A. A., 250,
659, 665
Coates, G. E., 76
Cochran, E. L., 36,617
Cocke, D. L., 81,235,
286
Cody, I. A., 318

Cody, V.,383
Coffy, G., 223
Cogneau, M., 629
Cohen, E. A., 141
Cohen, M. H., 20
Cohen, N., 465, 669
Cohen, R. B., 561
Cohn, K., 145,471
Coignac, J. P., 42
Cojocaru, L. N., 201
Cole, W. F., 609
Colliard, J. P., 358, 364
Collier, J. G., 8
Collin, R., 483
Collin, R. I., 80
Collin, R. L., 517, 524
Collins, P. H., 44, 308,
642
Collman, J. P., 389

Combes, R., 68
Combourieu, J., 251, 466
Comes, F. J., 678
Congiu, A., 207
Connick, R. E., 662
Connolly, J. W. D., 679
Connor, J. A., 143, 293
Conrow, K., 549
Constant, M., 246
Constantinescu, O., 541
Contreras, J. G., 214
Contreras, R., 498
Cook, A. G., 517
Cook, R. L., 606
Cook, S. H., 517
Cook, T. J., 282, 560
Cook, W. J., 91, 92, 512
Cook, W. L., 165, 166
Cooke, D. L., 198
Cool, T. A., 669
Coon, J. B., 607
Coombe, R. D., 651
Cooper, R., 283
Cooper, W.F., 157
Cope, V., 281
Coppens, P., 157
Copperthwaite, R. G.,
375
Corbett, J. D., 555

Corbridge, D. E. C., 523,
524
Corchia, M., 648

Cordes, A. W., 146,471
Corey, E. J., 383
Corfield, P. W. R., 126,
163,406
Corice, R. J., 607

Cormier, A. D., 466
Cornet, J., 649
Cornier, G., 184
Cornwell, C. D., 659
Corosine, M., 439
Corriu, R. J. P., 291
Costantino, U., 521
Costy, J. P., 43
Cot, L., 74, 490, 491,
612, 613
Cotton, F. A., 421

Cotton, S. A., 375
Coucouvanis, D., 309
Coughran, W., 431
Countess, R. J., 435
Courant, R. A., 568
Couret, C., 480
Couret, F., 480
Courtine, P., 527
Courtois, A., 425
Cousseau, J., 20
Cousseins, J. C., 43
Coustures, Y.,497
Couzi, M., 440
A uthor Index
Covington, A. K., 154
Cowan, D. O., 466
Cowley, A. H., 433, 483,
494
Cox, L. E., 308
Cox, D. E., 560
Coxon, J. A., 267, 659
Coyle, T. D., 255, 305
Cozzi, D., 667
Cradock, S., 292, 307,
392
Cradwick, M. E., 331
Cradwick, P. D. G., 338
Cragg, R. H., 168, 169
Craggs, J. D., 4
Craig, N. C., 444
Cramer, D. T., 548
Crasnier, F., 142, 439,
48 1
Creaser, I. I., 516
Creeden, J. E., 52
Creighton, J. A., 253, 272,
505, 579
Crernlyn, R. J. W., 501
Creyghton, J. H. N., 172
Crisler, L. R., 265
Cristophliemk, P., 278,
53 1, 626
Crociani, B., 399
Crocker, A. J., 649
Crook, M. F., 487
Crozat, M., 423
Crozat, M. M., 395
Cruickshank, D. W. J.,
658
Cruiziat, B., 103
Csanyi, L. J., 217
Cseh, F., 217
Csizmadia, I. G., 104,
256,494
Cuche, C., 218
Cueilleron, J., 103
Cvetanovic, R. J., 453
Cugley, J. A., 287, 436
Cugnac-Pailliotet, A.,
616
Cullen, W. R., 534, 537
Cunningham, J., 454
Cunningham, P. T., 3,
576, 624,648
Curien, H., 199
Currie, K. L., 335
Curry, J. D., 477
Curtis, E. C., 594, 664
Curtis, M. D., 418
Cusachs, L. C., 223
Cussler, E. L., 26
Cutforth, B. D., 538
Cuthill, A. hl., 198
Cyganski, A., 59
Cynkier, I., 52
Cyvin, B. N., 69, 195
45
691
Cyvin, S. J., 43, 69, 195,
473, 491
Czak is-Sulikow ska, D .
M., 222
Czamowski, J., 665
Czieslik, G., 373, 486,
490
Dabescat, F., 367
Dadape, V. V., 196
Da GraCa Cravierinha
Dillon, M., 264
Dahl, L. F., 392
Dahlmann, W., 467
Dailey, B. P.,480
Dakhis, M. I., 256
Dale, B., 392
Dale, J., 29
Dale, J. M., 574
DAlesio, E. A., 249
Dalla-Lana, I. G., 274,
607
Daly, F. P., 611
Daly, J. J., 477, 487, 535
Dalziel, J. R., 663
Damien, D., 533
Dammann, C. B., 398
Danchik, R., 100
Danzk, V., 193
Danen, W. C., 434
Dangre, A. J., 30, 90
Daniel, F. V. G., 369,
370
Daniel, M. Y., 79
Daniel, S. H., 402
Danilkin, V. A., 101
Dann, P. E., 497, 511
Danot, M., 21
Dao, N. Q . , 288
DAprano, A., 17
DArcollieres, F. C., 232
Darina, T. G., 44
Das, G. C., 425
Das, R. N., 507
Dashevskii, M. I., 298
Datar, D. S., 278
Daud, J.-M., 194
Dauksch, H., 230, 233
Daunt, S. J., 257
David, J., 48
Davidovics, G., 371
Davidovich, R. L., 149,
307, 547, 612
Davidson, D. W., 257,
483
Davidson, M. E. A., 141
Davidson, P. J., 421
Davies, C. G., 538
Davies, G., 655
Davies, H. A., 12
Davies, J. B., 672
Davies, J. E. D., 557
Davies, N., I12

Davies, R. D., 39
Davis, A. R., 278
Davis, D. D., 463
Davis, H. L., 555
Davison, A., 107
Davydov, V. A., 69
Davydov, V. Ya., 318
Davydova, T. S.,632
Dawson, P. H., 669
Day, J. P., 293
Day, M. C., 24
Day, V. W., 83
Dazhina, L. G., 199
Deacon, G. B., 558
Dean, P. A. W., 538,
547
de Angelis, G., 422
Dcaton, B. C., 230
Debaerdemaeker, T., 572
Debeau, M., 42
De Bleyser, J., 247
De Boer, B. G., 137
De Boer, E., 25
De Bolster, M. W. G.,
86,499
Decerf, J., 309, 518, 537
Decius, J. C., 287
Decyatnik, V. N.,
408
Deflin, M., 184
Deganello, S., 74
DeGiorgi, G., 648
De Haas, N., 267,463,
572
De Hair, J. T. W., 558
Dehler, O., 249
Dehmer, J. L., 213, 223,
665
Dehrner, P. M., 664

Dehnicke, K., 200,492,
558,658
Dei, A., 673
Deich, A. Ya., 656
Deichman, E. N., 209,
527, 629, 630
Deineka, G. F., 281
Deiseroth, H.-J., 202
Deitz, V. R., 233
De Kepper, P., 229
De Kock, R. L., 608,
660, 677
De Kozak, A., 71
Delahay, P., 20
DelaMatter, D., 477
De La Torre Cabezas,
M., 9
Delatari, N. V., 302
Delbaere, L. T. J., 537
Del Bene, J. E., 439, 674
Delhaes, P., 229
Delimer, J. L., 148
Della Gatta, G.,184
Author Index
692
Dellalian, M., 327
Della Monica, M. R.,
23
Delmaire, J.-P., 574, 584
Delmas, M., 371
Delorme, R., 243
Delpuech, J. J., 17, 185,
442
DeMarco, R. A., 465,
618
De Maria, G., 546
Demay, C., 486
Dembovskii, S. A., 542
Demenev, A. V., 209
Demidov, A. I., 11
Demore, W. B., 244,267
Demuth, R., 472,473,
474,533, 534
Demyanets, L. N., 351,
352
Den Heijer, J., 499
Dent Glasser, L. S., 188,
325
De Pena, R. G., 435
De Pieri, R., 337
Deppisch, B., 521
Derkacheva, V. N., 19
Deroche, J.-C., 243
de Rumi, V. B., 186
Deryagin, B. V., 227, 569
Desai, V. B., 511
de Sallier Dupin, A., 523
Desgardin, G., 558
Deshpande, S. G., 552
Desideri, A., 427
Desjardins, C. D., 162,
621
Desmarteau, D. D., 259,
490, 594, 613
DespotoviC, R., 224
Dessaux, O., 150
De Staricco, E. R., 160,
294
des Tombe, F. J. A., 399
Desyatnik, V. N., 71
Dettaan, A., 589
Deutsch, P. W., 242, 297
Dev, R., 540,558
DeVan, J. H., 7
Devarajan, V., 473
Devaud, M., 307, 358,
364
Devillers, J., 483
Devin, C., 455
De Vos, D., 363
de Vries, J. L. K. F.,
372
Devyatkin, V. N., 67
Dey, A. N., 3
Dezarov, I., 236, 468
Dhabanandana, S., 66
Dhar, S. K., 422
DHondt, J., 655

Diamond, R. M., 459
Dias, R. M. A., 222
Dibeler, V. H., 259
Dickens, B., 55, 542
Dickinson, R., 282, 446
Dickson, R. S., 178
Didych, M. N., 491
Dieck, R. L., 507
Diercksen, G. H. F., 438
Dieseroth, H. J., 88
Dietl, M., 529, 601
Dietrich, B., 27
Dietz, E. A., jun., 472,495
Dieva, E. N., 11
Dillon, K. B., 484
Dilmukhambetov, E. E.,
344
Dimitrov, A., 216
Dinesch, R., 341
Diogenov, G. G., 61,
461, 613
Diomedi-Camessei, F.,
574
Dion, M., 222
Dionisev, S. D., 224
Diot, M., 55, 578
Distefano, G., 394
Distefano, S., 372
Divjakovic, V., 76
Dixit, L., 205
Dixon, H. P., 44
Djega-Mariadassou, C.,
353
Dkruszek, A., 531
Dlouhy, Z., 59
Dmitrevskii, G. E., 43
Dmitriev, I. A., 75
Dmitriev, V. A., 584
Doak, G. O., 489, 533
546,555
Dobbers, J., 469
Dobbie, R. C., 474,485
Dobbs, F. R., 175
Dobramysl, W., 58
Dobrolyubova, M. S., 37
Dobrotin, R. B., 565
Dobrova, E. I., 304
Dobrowloski, J., 643
Docken, K. K., 676
Dodero, E., 249
Dodgen, H. W., 658
Doe, J., 421
Dolling, H., 667
Doemeny, P. A., 432
Doggett, G.,504
Dolhaine, H., 33
D o h , S. P., 151, 183,
277, 316, 519, 606
Dollomore, D., 230
Dombrovskaya, N. S., 18
Dombrovskii, N. M., 525
Dominelli, N., 394

Domnina, E. S., 315
Donaldson, J. D., 392,
407, 410,548, 554
Donato, I. D., 17
Dondes, S., 267
Dong, R. Y., 260
Donika, F. G., 211, 588
Donika, T. V., 588
Donnay, G., 157
Donnay, J. D. H., 157,
523
Donnet, J.-B., 230, 233,
238
Donohue, J., 671
Donohue, P. C., 468,469
Donovan, R. J., 45,634
Doolittle, J., 242
Dortmieux, C., 520, 540
Dortmieux-Morin, C.,
325, 328
Dorfeld, W. G., 273
Dorfman, L. P., 70
Dorfman, Ya. A., 431
Dori, Z., 447
Dorney, A. J., 608
Dorofeenk, L. P., 388
Dorofeeva, 0. V., 121
Dorogov, M. E., 281
Doronina, V. P., 72
Dorosh, A. I., 525
Dorosinskii, A. L., 180
Dostal, K., 519
Doucet, J., 246
Doucet, Y.,461
Douek, J. A., 314
Douglas, T. B., 194, 671
Douglas, D. C., 248
Dousse, G., 381
Downs, A. J., 621
Dows, D. A., 151
Dowty, E., 158
Doyle, M. P., 450
Drache, M., 203
Drager, M., 151, 531, 626
Dragulescu, C., 557
Dragulin, E. M., 409
Drake, J. E., 145, 291,
372, 382, 383, 470, 532
Drakin, S. I., 76
Dress, J., 83
Drew, D. A., 177
Drew, M., 179
Drexler, J.-P., 442
Dreyer, J. W., 450
Drobot, N. F., 303
Drobyshev, L. A., 354
Dronova, N. D., 184
Drouin, R., 650
Drozdova, 0. A., 11
Druelashvili, M. I. 429
Drummond, I., 589
Author Index
Drury, J. S., 225
Dryburgh, J. S., 292
Dubev, M., 235
Dubey, D. S., 33
Dublish, A. K., 205, 214
Duboc, C., 21
Duboudin, F., 367
Dubois, B., 203
Dubois, C., 455
Dubost, H., 266
Dubrova, E. F., 191
Dudarev, V. Ya., 37
Duderov, N. G., 352
Dudin, A. V., 567,665
Dudoreva, A. G., 215
Duewer, W. H., 296
Dufaux, M., 324, 566
Dugleux, P., 523
Dult, W., 440
Dumas, G. G., 253
Dumas, J. C., 369, 370,
475
Dumas, Y., 515, 524
DuMont, W. W., 382
Dumoulard, J.-P., 280,
455
Dunaevskaya, N. A., 519
Duncan, J. F., 326
Duncan, J. L., 246,254
Dunell, B. A., 306
Dunks, G. B., 117, 134,
136
Dunmore, P. V., 430
Dunn, M. B., 200
Dunn, O., 267
Dunn, R. L., 523
Dunster, M. O., 372, 389
Duplatre, G., 629
Dupont, M., 199
D u p e , G., 466
du Preez, J. G. H., 499
Durand, J., 490, 491
Durand, M., 538
Durand, P., 242
Durham, M. E., 5
Durif, A., 326, 522, 525,
526, 527, 528
Durif, M., 328
Durig, J. R., 142, 145,
150, 259, 265, 296,
305, 306, 383, 443,
470,473,474,491, 534
Durkin, T. R., 163
Durtschi, A., 422
Duryrnanova, M. A., 18
Dusausoy, Y., 570
Dusek, B., 192
Dustin, D. F., 125, 136
Dutchak, Ya. I., 426
Dutrizac, J. E., 575
Duyckaerts, G., 309, 518,
537
45A
693
Dyachenko, 0. Ya., 189
Dyachkova, N. N., 358
Dyakov, V. M., 361
Dyatkin, B. L., 402
Dyatkina, M. E., 151,
183, 277, 316, 460, 519,
606
Dyatlova, L. D., 370
Dye, J. L., 21, 28
Dyer, A., 345
Dymanus, A., 454
Dymock, K., 203
Dymova, T. N., 175
Dyroff, W., 500
Dyuzheva, T. I., 425
dYvoire, F., 520, 540,
542
Dzene, A., 158
Dzhagatspanyan, R. V.,
257
Dzhuraev, Kh. Sh., 42
Dzhurinskii, B. F., 157,
527
Dziomko, V. M., 59
Dzvonar, V. G., 298
Dzyuba, E. D., 522
Eables, T. E., 243
Eaborn, C., 365, 401
Eakers, C. W., 433
Easteal, A. J., 155, 408
Easton, D. S., 1
Ebeling, J., 508
Ebert, M., 516
Ebisuzaki, Y., 440
Ebsworth, E. A. V., 292,
392,398,490
Eckstein, G., 521
Ediseeva, 0. N., 257
Edmiston, C., 104,242
Edward, 0. W., 523
Edwards, A. J., 550
Edwards, J. O., 516
Edwards, L. O., 246
Edy, D. J., 155
Efskind, L., 571
Egerton, T. A., 344, 346
Eglington, G., 225
Egorov-Trisrnenko, Yu.
K., 87
Ehemann, M., 112
Eholie, R., 370
Ehrburger, P., 230, 233,
238
Eichhorn, B., 486, 533,
539
Eick, H. A., 238, 326
Eiletz, H., 502
Einstein, F. W. B., 208
Eisenberg, M., 613
Eisenhut, M., 488
Eisenmann, B., 96
Eisner, E., 394

Elchin, E. A., 19
Elenkova, N. G., 540
El-Gad, U., 661, 679
El-Garhy, M., 208
Eliezer, I., 81
Elliott, G. R. B., 427,
429
Elliott, L. E., 294, 479
Ellis, I. A., 301, 302, 314,
450
Ellis, P. D., 105, 106
Ellmer, J., 426
Ellsworth, R. L., 463
El Maslout, A., 48
El-Meligy, M. S. A., 364
Elnatanov, Yu. I., 472
Elphingstone, E. A., 481,
490, 620
El Sawy, S., 189, 340
El-Shamy, H. K., 408,
518
Elter, R., 588
Emeleus, H. J., 596
Emelin, V. P., 498
Emerson, J. A., 353
Emken, W. C., 596
Emmerson, D. S., 523,
524
Emons, H. H., 65
Emsley, J., 487
Enders-Beumer, A,, 263
Endo, F., 615
Endo, J., 174
Endo, Y., 236
Enemark, J. H., 169
Engel, G., 523
Engelbrecht, A., 673
Engelmann, Ch., 560
England, W., 256
Englehardt, U., 466
Englin, M. A., 358
Ennan, A. A., 16
Entner, P., 370
Epimakhov, V. N., 88,
438
Epperlein, J., 522
Epstein, G. L., 10
Epstein, J. A., 458, 672
Epstein, I. R., 105, 121
Erdos, E., 97, 612, 615
Eremin, E. R., 196, 334
Eremin, N. I., 334
Erenburg, A. I., 249
Ergun, S., 228, 230
Ermolenko, N. F., 344
Ertl, G., 270
Ershova, Z. V., 75, 61 1
Escard, J., 233
Eshchenko, L. S., 522
Esin, 0. A., 335
Esirkegenav, G. M., 351
694
Esperhs, S., 223, 645
Estacio, P., 294, 479
El Baragy, M., 198
Etienne, J., 176, 212, 369
Etourneau, J., 171
Ettmayer, P., 435
Eujen, R., 51, 425
Eulenberger, G., 216,
223, 531, 625, 643, 648
Evans, C. A., 205
Evans. D. A., 49, 610
Evans, D. F., 26
Evans, E. L., 233
Evans, H. E., 8
Evans, H. T., jun., 519
Evans, R. M., 424
Evans, W. J., 110, 117
Evdokimov, V. I., 103,
150, 303,482
Evstifeev, E. N., 194
Evstropev, K. K., 65
Evzhanov, Kh. N., 3
Evzhanov, Kh., 6
Ewool, K. M., 248
Eyring, H., 274
Ezhov, A. I., 182, 215,
350
Ezhov, V. K., 549
Ezhov, Yu. S., 45, 155,
612
Ezra, F. S., 80, 517
Fabian, D. J., 198
Facetti, J. F., 583
Fadeeva, V. I., 458
Fadini, A., 491
Fagone, F. A., 226
Fahr, E., 450
Faivre, M., 243
Falconer, J. N., 244
Falconer, W. E., 549
Falgueirettes, J., 264, 524
Falius, H., 373, 467, 486,
490,513
Falk, M. V., 671
Falkenberg, G., 355
Fallon, G. D., 558
Fally, J., 9
Fang, J. H., 191
Fano, U., 148
Farmer, C. B., 463
Farmer, V. C., 338
Farnworth, E. R., 261
Farr, T. D., 523
Farrell, E. F., 569
Farrell, N., 365
Fsitu, D., 279
Faucher, J.-P., 506
Fauquembergue, R., 246
Faurie, J.-P., 554
Fay, E., 350
Feather, D. H., 204, 220
Author Index
Feather, R., 2
Fedorenko, T. P., 18,
192, 613
Fedoritenko, I. I., 191
Fedorov, L. A., 306
Fedorov, N. F., 93, 327,
336, 354,365,523
Fedorov, P. I., 205,215,
625
Fedorov, P. M., 44,210
Fedorov, P. P., 205
Fedorov, V. A., 224, 556
Fedorova, L. F., 101
Fedoryako, L. I., 279
Fedoseev, D. V., 227
Fedotov, A. F., 325
Fedyaev, N. I., 215
Feher, F., 290, 574
Fehlner, J. R., 364
Fehlner, T. P., 108, 152,
160,424
Feilchenfeld, H., 458, 672
Feistel, G. R., 507
Feldman, D. W., 352
Feldmann, W., 525
Feldt, M. K., 507
Feltz, A., 626, 644, 649
Fenby, D. V., 253, 439
Fenger, J., 516
Fenn, J. B., 441
Fenske, D., 479
Fenton, D. E., 29
Fenwick, J. T. F., 152
Feoktistova, N. N., 554
Ferguson, G., 535
Ferguson, K. C., 254
Fergusson, J. E., 544
Fermor, J. H., 459
Fernando, W. S., 505
Ferradini, C., 617
Ferrar, I. J., 441
Ferraris, G., 80, 542
Ferris, C. M., 555
Feshchenko, N. G., 493
Fessenden, R. W., 283,
614
Fetter, N. R., 600
Feughelmon, M., 230
Fey, G. T., 486
Fialkov, Yu. Ya., 550
Field, R. W., 454
Figusch, V., 187
Filatov, S. K., 610
Filby, E. E., 79, 235
Fild, M., 488
Filimonov, V. N., 270,
274
Filippov, E. A., 509
Filippov, V. IS.,19
Filippov, Yu. V., 272
Filonenko, L. P., 377
Filyagina, N. A., 59
Finch, A., 196

Fink, D., 210
Finkbeiner, H. C., 198
Finkelshtein, N. A., 68
Finkelshtein, Ya. G.,
587
Finkenauer, H. J., 100
Finney, A. A., 40
Finogenova, V. K., 53
Firsanova, L. A., 416
Fischer, A. K., 6
Fischer, G., 78
Fischer, M., 592
Fischer, R., 372
Fischer, W., 82
Fisk,Z., 95
Fiskander, M., 518
Fitzgibbon, G. C., 97
Fitznor, K., 427
Fitzpatrick, N. J., 148
Flack, H., 615
Flahaut, J., 89, 369, 370,
585, 626, 647
Flaskerud, G., 313, 490
Flatau, G. N., 486
Flechon, J., 442
Fleet, B., 560
Fleet, M. E., 545, 559
Fleischmann, M., 651
Fleming, S., 494
Flick, W., 494
Flid, R. M., 257
Flor, G., 63
Flora, H. B., 24
Floriani, C., 32,440
Flotow, H. E., 50
Floyd, G. R., 569
Fluck, E., 315, 446,469
487, 495,496, 501, 529,
530, 592,604
Flygare, W. H., 265, 284
Flynn, G. W., 591
Focke, B., 649
Foct, J., 202
Forster, M., 544
Foester, R., 145, 471
Foffani, A., 394
Folli, U., 359
Follner, H., 153, 361
Fomichev, V. V., 546,548,
549
Fomicheva, M. G., 498
Fomichov, A. A., 472
Fomina, N. V., 299, 304
Foner, S.N., 465
Fong, F., 372
Fontal, B., 482
Foord, A. D., 232
Forbes, C. P., 666
Forder, R. A., 178
Ford-Smith, M. H., 558
Forel, M. T., 170, 499
Author Index
Foresti, M. L., 667
Forgaard, F. R., 176
Fornier de Violet, P., 652
Foroughi, K., 517
Forsellini, E., 276
FOSS,
O., 645
Fouassier, C. 87, 158
Fouassier, F., 158
Fouassier, M., 170
Fouche, K. F., 208
Fourcade, R., 149,458
Fourdeux, A., 239
Fournbs, L., 224
Fournier, J., 435
Fox, IS.,243,607
Fraas, L. M., 187
Frainnet, E., 367
Fraissard, J., 521
Frame, H. D., 681
Franceschi, E., 88,467
Francia, M. D., 469
Franchini-Angela, M.,
80,542
Francis, M. F., 126
Frange, B., 162, 166
Frank, U., 372
Franke, E. R., 95,198,
648
Franklin, J. L., 193, 307
Franzini, M., 337
Fraser, W., 591
Fraser, W. L., 440
Frazier, R. H., jun., 432
Frazzoli, F. V., 59
Fredericks, M., 63, 609
Fredin, L., 654, 655
Fredrickson, D. R., 35
Freedman, L. D., 533,
546,555
Freeman, G. R., 251
Frees, G., 7
Freese, J. M., 226,228
Frei, V., 557
Freidel, R. A., 230
Freik, D. M., 427, 648
Frembs, D. W. R., 366
Fremont-Lamouranne,
R., 235
Frenchko, V. S.,426
Frentrup, K. R., 339
Freude, D., 219
Freund, E., 325, 328,
334
Freund, R., 290
Freund, T., 564
Frey, C. M., 84
Fridh, L., 287
Friedman, 13. L., 13, 21
Friedman, L. B., 109
Friedman, R. M., 555
Friedrich, F., 278, 629
Friedrich, H. B., 450
695
Friedt, J. M., 315
Fries, J. 317
Frieson, D. K., 315
Frings, H., 290
Frit, B., 558, 636
Fritchie, C. J., 371, 579
Fritz, H. P., 41, 149
Fritzby, H. G., 433
Fritzer, H. P., 58, 188
Frlec, B., 661, 677
Froede, H. C., 490
Frayen, P., 540
Frolkova, S. A., 43
Frolov, A. A., 427
Frolov, I. A., 290
Frost, D. C., 265, 595
Frost, J. J., 295
Fruchart, E., 237
Fruchart, R., 237
Frydrych, R., 367, 667
Fu, Y. C., 268
Fubini, B., 184
Fueno, T., 282
Fuhr, B. J., 422
Fujii, T., 615
Fujimoto, H., 439
Fujimoto, T., 257
Fujinaga, T., 23
Fujiwara, M., 258
Fujiwara, S., 213
Fujiyama, T., 257, 272
Fukanovb, P., 519
Fukuda, N., 575
Fukuda, Y., 274
Fukui, K., 439
Fukumoto, T., 530
Fukushima, IS., 440
Fukushima, R., 248
Fuller, M. J., 268, 422
Fung, K. W., 546
Furergendler, S. I., 227
Furimsky, E., 514
Furstenberger, R., 233
Furukawa, J., 424
Furukawa, K., 5
Furukawa, Y., 197, 215
Fuwa, K., 213
Fuzellier, H., 241, 668
Gaal, I., 536
Gabes, W., 484, 662
Gabor, G., 21
Gabuda, S. P., 338
Gadet, M.-C., 616
Gaedtke, H., 463
Gagnaire, D., 470
Gaiduchok, G. M., 427,
648
Gaillard, J., 541
Gailor, N. M., 569
Gaines, D. F., 114, 115
Gaiser, V., 186
Gaite, J. M., 328

Gal, S., 81
Galantseva, M. L., 353
Galasiu, I., 408
Galerie, A., 409
Galigne, J.-L., 264, 515,
524
Galimov, E. M., 227
Galitskii, V. Yu., 338
Galiullina, R. F., 357
Gallagher, P. K., 96, 363
Gallaher, K. L., 119
Gallais, F., 146, 471
Gallezot, P., 344, 346
Gallon, T. E., 80
Galstyan, V. D., 18
Galy, J., 201, 644
Gamayurova, V. S., 536
Gambino, M., 12
Gamidov, R. S., 625
Gangulee, A., 425
Ganguli, P. S., 462
Gangwer, T., 462
Ganne, M., 220,521
Gar, T. K., 299
Garbassi, F., 517
Garcia-Blanco, S., 498
Garcia-Fernandez, H., 603,
634
Gard, J. A., 47
Gardiner, D. J., 23, 83,
437, 568, 664
Gardner, J. L., 430,454
Gardner, M., 528,573,581
Gardner, P. J., 196
Garg, S. K., 257, 483
Garifdzhanova, N. M., 608
Garin, J., 532
Garnovskii, A. D., 394
Gasan, V. M., 249
Gasanov, G. Sh., 619
Gasanova, E. L.,208
Gascard, C., 149
Gash, A. G., 307
Gashpur, E. D., 281, 289
Gaspar, P. P., 295, 296
Gasparoux, H., 229
Gass, J. L., 184
Gatehouse, B. M., 276
Gather, B., 628
Gatilov, Yu. F., 535, 536,
544
Gaudreau, B., 43
Gaumann, A., 628
Gaupp, A., 1
Gaur, D. P., 360, 361
Gautam, M. S., 4
Gautchenko, V., 174
Gavrilenko, V. V., 56, 87,
175
Gavrilov, K. A., 60
Gavrilov, V. I., 535, 537
696
Gavrilova, G. R., 535
Gavrilova, S. S., 77
Gay, R. S., 482
Gayoso, J., 161
Gazner, A. P., 189
Gazzoni, G., 188
Geanangel, R. A., 142
Gearhart, R. C., 308
Gebert, W., 188, 524
Geddes, J., 273
Gedymin, V. V., 133
Geffroy, J., 542
Gehin, C., 54, 240
Geisler, I., 144, 374
Geisler, T. C., 106, 386
Geissler, H., 306
Gelbshtein, A. I., 274
Geld, P. V., 236, 427
Gelius, U., 104, 271, 578
Gellings, P. J., 409
Gelus, M., 104
Gennaro, G. P., 402
Gennis, M., 677
Genser, E. E., 662
Geoffroy, M., 530
George, J. W., 151, 641
George, R. D., 395
George, T. A., 393
George, W. O., 383
Georgescu, N., 62, 459,
669
Gerasimenko, L. N., 11
Gerasimenko, V. S., 626
Gerasimov, Ya. I., 52, 73
Gerbaux, X., 634
Gerding, H., 358, 371, 484
Gerl, H., 97
Germain, J. E., 423
German, A. M., 492
Geroleva, 0. V., 19, 613
Gerorkyan, S. V., 617
Gerry, M. C. L., 282
Gertl, H., 644
Gerzhberg, Yu. I., 23, 24
Gethin, A., 452
Getman, E. T., 192, 210
Geuson, D. W., 433
Gevorkyan, S. V., 184
Ghandi, D. L., 231
Ghetsch, J., 184
Ghormley, J. H., 463
Ghose, S., 337
Ghosh, A., 429
Ghosh, T. K., 74, 75
Ghotra, J. S.,375
Ghouse, K. M., 502
Giacovazzo, C., 186
Giarda, L., 517
Gibby, M. G., 441
Gibler, D. D., 592, 677
Gibson, J. A., 306, 483,
661, 678
Author Index
Gibson, J. F., 375
Giese, R. F., 157
Giesen, K. P., 373, 513
Giganov, G. P., 635
Gigauri, R. D., 535
Giggenbach, W. F., 588
Gigli, G., 237
Gigli, R., 546
Giguere, J., 272
Giguere, P. A., 564
Gilbert, B., 309, 518, 537
Gilbert, M. M., 208
Gilbert, R., 246
Gilje, J. W., 598
Gilkerson, W. R., 24
Gill, J. B., 438, 614
Gillbro, T., 596
Gillen, K. T., 248
Gilles, L.,666
Gillespie, P., 516
Gillespie, R. J., 284, 537,
538, 547, 616, 617, 622,
659,670, 672, 677, 679
Gillies, G. C., 556
Gilyarov, V. A., 501
Gimarc, B. M., 104
Ginderow, P. D., 367
Gingerich, K. A., 11, 81,
198,235, 286.468, 545
Gingold, M. P., 569
Ginns, I. S., 288, 617
Ginzburg, A. G., 3 15
Giovenco, A., 367
Giraud, D., 355
Girling, R. B., 83
Gitis, E. B., 191
Gjerrestad, K., 646
Gladis, K., 215
Gladkii, V. V., 519
Gladyshev, E. N., 401,402
Gladyshev, V. P., 12
Gladyshevskii, E. I., 78,
427
Glanzer, K., 445
Gleiter, R., 466
Gleitzer, C., 48
Glemser, O., 373, 378,466,
486, 490, 506, 513, 568,
596
Glick, M. D., 383
Glicker, S., 148, 435
Glinka, K., 529
Glasgow, L. C., 251, 652
Glasser, F. P., 187, 188
GIasser, L. S. D., 96
Glass, G. P., 562, 671
Glazunov, 0. O., 611
Glockling, F., 385, 392,
398
Glore, J. D., 159
Glushchenko, E. L., 208
Glusker, J. P., 33
Glybovskaya, V. A., 315

Gnauck, G., 677
Gnehm, Ch., 212, 559,585
Go, M. K., 570
Goates, J. R., 11, 253
Goba, V. E., 231
Goddard, W. A., tert., 104
Gode, G. K., 19, 154
Godel, D., 78
Godet, M., 198
Goel, R. G., 546, 555
Goetz, G., 547
Gotz, J., 539
Gold, K., 128
Goldberg, H. S., 248
Goldberger, I., 416
Goldanskii, V. I., 314
Goldman, A., 649
Goldschmidt, J. M. E.,
505
Goldshtein, I. P., 640
Goldstein, M., 151
Goldwhite, H., 372
Gole, J. L., 74
GoIik, G. A., 503
Golino, C. M., 384
Goloshchapov, M. V., 522
Golovanov, V. I., 199
Golovei, M. I., 587
Goltyapin, Yu. V., 133
Golub, A. M., 202
Golub, L., 649
Golubeva, N. D., 50, 175
Golubtsov, S. A., 297,
298, 355
Golyshev, V. M., 329
Gonzalez-Quintana, J. A.,
186
Good, M. L., 214, 556
Goodall, D. C., 614
Goodall, D. H. J., 2
Goodenough, J. B., 553
Goodfriend, P. C., 481
Goosen, A,, 666
Goost, L., 406
Gopal, R., 527
Gorbatyi, L. V., 632
Gorbenko, F. P., 83, 101
Gorbov, S. I., 73
Gorbunov, A. I., 298
Gorchinskii, Ya. I., 623
Gordeev, A. D., 503
Gordienko, V. I., 203
Gordon, D. E., 230
Gordon, D. T., 287
Gordon, M. D., 556
Gordon, M. S., 256
Gorelik, M. V., 206
Gorelov, I. P., 211, 219,
220
Gorenbein, E. Ya., 92
Gorenstein, P., 649
Author Index
Gorogotskaya, L. I., 609
Gorokhov, L. N., 97
Gorse, R. A., 267, 572
Gorter, E. W., 42
Goruchov, O., 425
Goryacheva, V. G., 222,
613
Goryaev, V. M., 620
Gosling, K., 180, 371, 486
Gosney, I., 539
Gospodinov, G. G., 582
Gosset, J., 560
Goto, T., 4
Goubeau, J., 479, 493
Goudand, P., 150
Gourdon, J.-C., 562
Goursat, P., 355
Goutier, D., 148
Govaerts, F., 655
Govil, P. K., 187
Gowlenlock, B. G., 652
Goymour, C. G., 270
Gozhdzinskii, S. M., 202
Grabenstetter, R. J., 477
Grabke, H. J., 234
Gracey, H. E., 24
Graeber, E. J., 425
Grager, M., 278
Graffeuil, M., 143,443
Graham, C. D., 426
Graham, J. G., 507
Graham, R., 458
Graham, R. F., 454
Graham, W. R. M., 237
Grakova, I. V., 46
Gramlich, V., 521
Graner, G., 243
Granier, W., 490,491
Grannec, G., 222
Grannec, J., 43, 218
Grant, R. W., 427
Grashchenkova, L. N.,
231
Grasnier, F., 147
Gratch, S., 9
Graumann, A., 554
Gravelle, P. C., 268
Graves, A. D., 61
Graves, G. E., 490
Grayson, M., 477
Graziani, R., 276
Grebenshchikov, R. G.,
336, 352
Green, B., 505, 506
Green, D. W., 433
Green, M., 131
Green, M. L. H., 178
Green, R. D., 17
Greenberg, J. H., 212
Greenhalgh, R., 494
Greenler, R. G., 270
Gregor, V., 132
697
Grein, F., 162
Greiver, T. N., 637
Grenier, J.-C., 525, 528
Grenon, M., 5
Gribova, E. I., 67
Gridasova, R. K., 350
Gridina, V. F., 388
Griffin, L. L., 256
Griffin, R. G., 441
Griffiths, D. A., 427, 429
Griffiths, J. E., 248, 257
Griffith, E. H., 307
Griffith, E. J., 477
Grigorev, A. I., 76, 200,
205
Grigorev, A. P., 156
Grigorev, Ya. M., 274
Grigorovich, Z. I., 75, 668
Grigos, V. I., 133, 386
Griller, D., 514
Grillet, Y., 235
Grimes, R. N., 114, 120,
121, 122, 123, 388
Grimm, F. A., 245, 307
Grimmer, A.-R., 484
Grimvall, S., 410
Grinberg, S. B., 257
Grinberg, Ya. Kh., 625
Grinko, L. S., 61, 461
Grinko, V. A., 641, 642
Grinstead, R. R., 101
Grischenko, A. S., 310
Grishukov, V. A., 40
Grizik, A. A., 608
Grjotheim, K., 65, 66,
68, 194
Grobe, J., 382, 472, 473,
474,480,533, 534
Grodzicki, A., 206
Groeneveld, W. L., 86,
499
Groenvold, F., 68, 81
Gromov, U. V., 611
Gropen, O., 142
Gross, K. P., 121
Gross, M. H., 105
Gross, U., 657
Grossman, W. E. L., 23,
437
Groult, D., 554
Grout, P. J., 272
Gruen, D. M., 433
Gruntfest, M. G., 394
Grunze, H., 302,491,493
Grunze, I., 491
Grutsch, P. A., 424
Grzhegorzhevskii, A. S.,
101
Grzhikhova, R., 352
Gudaitis, M., 71
Gudim, L. I., 16
Gudz, V. S., 310
GuQin, H., 235, 542, 545,

585
Guest, M. F., 118, 143,
150, 307,466,469
Guggenberger, L. J., 177,
186
Guidelli, R., 667
Guido, M., 237
Guigueno, M., 427, 532
Guillermet, J., 83,439,613
Guillory, W. A., 261, 406
Guitel, J. C., 527
Guittard, M., 89, 206,223,
625
Gullman, J., 468
Gulyaeva, N. A., 485
Gunderloy, F. C., 659
Gundersen, G., 180
Gunning, H. E., 294
Gunther, O., 588
Gupalo, A. P., 529
Gupta, B. D., 315
Gupta, C. M., 422
Gupta, K. P., 427
Gupta, M. P., 33
Gupta, S. K., 589
Gupta, Y. K., 217, 552
Guroshko, L. V., 231
Guryanova, E. N., 206,
308,640
Gusarov, A. V., 97
Guseinov, G. D., 625
Gusev, A. I., 394
Gusev, S. I., 199
Guseva, R. P., 203
Gustyakova, M. P., 656
Gutmann, V., 499
Guttler, H. J., 5 8 8
Guyader, J., 427, 532
Guzei, L. S., 78
Guzhavina, T. I., 271, 579,
606
Gvildis, A. T., 86
Gynane, M. J. S., 215
Gysegem, P., 372
Gyunner, E. A., 18
Gyurov, G., 171
Ha, B.-H., 346
Haaland, A., 142,176,177,
178, 180
Haas, A., 261, 599
Haas, H., 188
Haase, A., 94, 545
Haase, J., 123
Haase, W., 538, 550, 674
Habboush, D. A., 64
Habeeb, J. J., 208,215,558
Habgood, H. W., 346
Hacker, H., 173
Hackett, P., 393
Haddon, W. F., 371
698
Hadek, V., 21
Hadizuana, J., 649
Hadni, A,, 634
HadZi, D., 674
Hldicke, P., 290
Hagele, G., 529
Haensel, R., 4, 678
Htinssgen, D., 378
Haga, N., 337
Hagen, A. P., 48 1,490,620
Hagenmuller, P., 171, 222
Hagihara, H., 414
Hagman, R. E., 64
Hahn, H., 216, 223, 531,
635, 643,648
Hahn, Th., 74
Haines, L. 1. B., 151
Haines, R. G., 486
Haines, W. J., 256
Hair, M. L.,321, 323
Haissinsky, M., 682
Haizlip, A. D., 296
Haldar, B. C., 216
Halicz, L., 457, 668
Hall, C., 61, 658
Hall, D., 205, 396, 397
Hall, H. T., 198,425
Hall, J. R., jun., 105, 113
Hall, K. E., 426
Hall, M. B., 150, 307, 469
Hall, R. B., 418
Hall, R. I., 430
Hall, W. R., 473
Hallam, H. E., 249, 672
Haller, W., 529
Hallmark, M. R., 444
Halm, H., 625
Hameka, H. F., 473
Hamilton, W. C., 112
Hammerle, R. W., 212
Hammond, S. K., 444
Hamon, C., 88,468
Hampshire, M. S., 625
Hamrick, P. J., 462
Hancock, G.,266, 273
Hancock, K. G., 140
Handa, Y., 615
Handlovic, M., 515
Handt, J., 605
Hanke, R., 638
Hannaker, R. M., 259
Hanousek, F., 109, 132
Hanrahan, R. J., 251
Hansen, F. V., 129
Hansen, H. D., 168
Hansen, J. E., 10
Hanson, T. E., 656
Hanssgen, D., 597
Hansson, I., 155
Hanzlik, T., 108, 132,
133
Haraguchi, H., 213
Author Index
Hardel, K., 409
Hardin, A. H., 569
Hardwick, J. L., 456
Hargreaves, R. N., 94
Harkema, S., 263
Harker, A. B., 463
Harland, P. W., 193, 258,
307,473, 501,622
Harman, B. R., 294
Harmon, T. C., 626
Harper, D. C., 519
Harris, D. H., 393
Harris, D. O., 282
Harris, L. E., 458,462
Harris, P. S.,232
Harris, R. K., 297, 504,
529
Harris, R. O., 431
Harris, W. C., 250, 443
Harrison, B., 457
Harrison, J. F., 433
Harrison, L. G., 461
Harrison, P. G., 313, 367,
371, 381,413, 421
Harrison, S. W., 675
Harrison, W., 511
Harshbarger, W. R., 243,
246
Hart, B. T., 447,464
Hart, E. J., 244
Hart, F. A., 375
Harteck, P., 267
Hartman, J. S., 141, 152,
170
Harvey, K. B., 569
Harzdorf, C., 102
Hasan, M.,506
Hase, W., 79
Hase, W. L., 295
Hasegawa, A., 274
Hasegawa, K., 79,192,525
Hasegawa, S., 19
Hashizume, G., 279
Hassanein, M., 189, 340
Hasselbach, K., 409
Hassiff, G., 268
Hastie, J. W., 64, 562
Hatano, Y.,452
Hatfield, J. D., 523
Hatibarau, J., 34
Haubold, W., 496,501,604
Hauft, R., 551
Hauge, R. H., 46, 50,286,
405
Haugen, T.,180
Haugeroed, O., 65
Haupt, H. J., 386
Hausen, H. D., 605
Hauser, A., 219
Hauser, C., 566
Hauser, P. J., 21 1
Havel, J. J., 226
Hawke, W., 323

Hawley, C. W., 306
Haworth, D. T., 161
Hawthorne, J. D., 521
Hawthorne, M. F., 110,
117, 125, 126, 128, 131,
134, 135, 136, 138, 139
Hayafuji, Y.,248
Hayashi, H., 79
Hayashi, S., 570
Hayes, E. F., 74
Hayes, R. G., 381
Hayward, E. J., 245
Hazel, J. P., 517
Hazell, R. G., 129
Heal, G. R., 230
Healy, P. C., 278
Hebecker, C.,218,223
Heber, R., 635
Hedberg, K., 596
Hedley, A. B., 435
Heess, R., 306
Heicklen, J., 258,267,435,
445,464,564
Heider, R., 574
Heilbronner, E., 466
Heintz, E. A., 232
Heitsch, C. W., 500
Heitz, C., 682
Hellman, T. M., 445
Hellner, E., 572
Hellwinkel, D., 445, 535
Hemmings, J. A. G., 151
Hemmings, R. T., 291,383
Hemsworth, R. S., 434
Henbel, J., 608
Hencher, J. L., 594
Hencken, G., 388
Hendrickson, D. N., 286
460
Hengge, E., 169, 290,291
385,386
Henis, J. M. S., 295
Hennequart, A., 9
Henriksen, L.,626
Hensen, K., 242,297
Herak, B., 632
Herak, M. J., 199
Herbelin, J. M., 465
Herber, R. H., 306, 363,
372, 388
Herbstein, F. H., 416
Hercules, D. M., 308, 503
Herd, A. C., 344
Herglotz, H. K., 39
HCrinckx, C., 239
Herlem, M., 574
Herlemont, F., 247
Herm, R. R., 250
Herman, J. A., 669
HeFmhnek, S., 108, 109,
125, 127, 128, 132, 139
Author Iridex
Hkrold, A., 53, 54, 239,
240,241,668
Herpin, P., 179

Herring, F. G., 592, 595
Herron, J. T., 463
Herschbach, D. R., 303,
652
Hertel, H., 544

Herter, R. M., 249
Hertl, W., 320, 321, 323
Hertz, R. K., 113
HBry, B., 542
Hess, H., 168, 605
Hester, R. E., 23, 83, 437
Heubel, J., 56
Hewson, M. J. C., 486,488
Heyding, R. D., 555, 636
Heyer, W., 155, 323
Heymer, G., 467
Heyns, A. M., 483
Heyrovsky, M., 574
Hickel, B., 666
Hickman, R. G., 2
Hiebl, H., 352
Hietanen, S., 522
Higashiyama, T., 19
Higginson, B. R., 650, 660
Hildenbrand, D. L., 35,
183, 591
Hiles, R. A., 412

Hill, K. W., 454
Hillel, R., 170, 590
Hillier, 1. H., 118, 143, 150,
307,466,469
Hills, G. J., 60, 61

Hilton, J., 364
Hijikata, K., 341
Hijikigawi, M., 248
Hinchen, J. J., 669
Hindman, J. C., 681
Hinks, D. G., 50,286
Hippler, H., 463
Hirabayashi, K., 423
Hirai, H., 258, 311
Hirata, J., 60
Hirokado, M., 615
Hirota, E., 665
Hirsbrunner, W., 100
Hirsch, R. G., 267, 272
Hisar, R. S., 526
Hisatsune, I. C., 450, 564
HjertBn, I., 221
Ho, B. Y.K., 362
Hoard, J. L., 83
Hoare, D. E., 244
Hobday, M. D., 201
Hobdell, M. R., 9
Hoberg, H., 182
Hochanadel, C. J., 463
Hocking, N.H., 282
Hodge, B., 4
Hodges, H. L.,471
699
Hodgson, K. O., 31
Hoebbel, D., 334
Hofer, R., 373, 378, 490
Hofler, F., 290, 301, 385,
474,534
Hoeft, J., 194, 198

Hogfeldt, E., 522
Hohn, B., 544
Hoel, E. L., 135
Hoell, J. M., jun., 454
Hoffman, M. Z., 281
Hofstotter, H., 146, 472
Hogen-Esch, T. E., 95
Hogg, J. H. C., 212, 625
Hoh, D. M., 552
Hohlneicher, G., 430
Holcombe, C. E., 45
Holdaway, M. D., 188
Hollander, F. J., 85, 86, 89
Hollas, J. M., 452
Holley, C. E., 97
Holliday, A. K., 131
Holloway, J. H., 661, 677,
679
Holm, B. J., 68, 69, 194

Holm, J., 82
Holm, J. L., 66, 68, 69,
193, 194
Holm, L., 81
Holm, R., 433
Holmberg, B., 64
Holmes, J. T., 6
Holmes, R. R., 483, 486
Holt, E. M., 596
Holt, S. L., 596
Homer, J. B., 409
Hon, J. F., 658,664
Honda, K., 258,445
Honerjager, R., 223
Hooper, H. O., 155
Hooper, M. A., 549
Hooley, J. G., 241
Hope, H., 51, 461
Hopf, G., 623, 635
Hopf, V., 11
Hopfgarten, F., 245
Hopkins, A. G., 562
Hopkins, H. P., jun., 175
Hopkins, J. M., 589
Hoppe, R., 46, 56, 58,
194, 210, 325, 327, 351,
353,409,460,558
Hora, C. J., jun., 483
Horn, F., 495,496
Horn, H.-G., 481
Horn, J., 278, 618
Horner, R. A., 568
Hosaka, A., 296
Hosaka, H., 324
Hougen, J. T., 436
Houriez, J., 247
Houser, T. J., 665
Houston, P. L., 150

Houston, R. E., 385, 398
Housty, J., 360
Howard, B. J., 455
Howard, J., 120, 395
Howard, J. A., 514
Howard, W. F., 652
Howatson, J. H., 483
Howells, J. D. R., 249,672
Howie, R. A,,405,410,412
Howlett, D. R., 44
Howlett, K. D., 502, 530
Hoy, A. R., 608
Hoyano, J., 389
Hoyer, E., 635
Hsu, C. C., 11
Hsu, C. M., 311
HSU,S.-C., 679
Hu, V. W., 598
Huang, W. H., 341
Huang, Y.,274,346
Hubbard, C. R., 548
Hubbard, W. N., 50
Huber, E. J., 97
Huber, F., 308, 364, 365,
386
Huber, H., 432

Huber, M., 367
Hudgens, B. A., 145,470
Hudson, J. B., 273
Hudson, R. F., 494
Hudson, R. L., 465
Huffman, J. C., 109
Hughes, B. M., 274
Hughes, I. L., 219
Hughey, J. L., 398
Hughson, M. R., 10
Huheey, J. E., 308
Huie, R. E., 463
Hull, J. R., 452
Hull, L. A., 564
Hulliger, F., 532
Hulme, R., 284, 670
Hunt, G. W., 146,471
Hurdus, M. H., 638
Hursthouse, M. B., 375
Husain, D., 45
Husband, J. P. N., 169
Husebye, S., 223, 645
Husson, E., 413
Huston, J. L., 682
Hutchinson, R. W., 418
Hutchinson, S. E., 532
Huyton, D. W., 590
Hwang, J. T., 38, 561
Hyatt, C., 129
Hyman, H. H., 44,557,659
Hyskens, P., 655
Iandelli, A., 88, 198,467
Iarossi, D., 359
Tato, V. P., 482
700
Ibaiiez, F., 529, 592
Ibbott, D. G., 483
Ibers, J. A., 217, 593
Ievins, A., 53, 158
Iglesias, J. E., 96, 370,
587, 626, 628
Ihara, M., 93
Ihlefeld, H., 440
Ihrig, P. J., 565
Iitaka, Y., 29
Ikeda, M., 248
lkeda, S., 60,263, 669
Ikezawa, M., 566
Ikonnikov, A. A., 556
Ikrami, D. D., 42
11-Hyun Park, 441
Ilichev, V. A., 67
Win, E. G., 656
Ilina, T. S., 111
Ilinskaya, E. P., 281
Ilyashenko, V. S., 613
Ilyasov, I. I., 461
Ilyukha, N. G., 188
Ilyukhin, V. V., 327, 351
Imai, T., 346
Imanov, R. M., 223
Imlach, J. A., 188
Imelik, B., 344, 346
Imprescia, R. J., 228
Tngle, W. M., 395
Ingold, K. U., 514
Inman, D., 61
Inman, F. W., 40
Inokuchi, W., 561
Inoue, T., 516
Ioffe, L., 159
Ionkina, E. A., 521
Ionov, L. B., 535, 536
Ionov, V. M., 515
Iosif, I., 244
Ippolitiv, E. G., 71
Iqbal, Z., 219, 288, 449
Ireland, P. R., 538
Irinei, F., 18
Irish, D. E., 61, 459
Isa, S. A., 451
Isaacs, T. J., 625
Isabaev, S. M., 53, 581,
584
Isabel, R. J., 406
Isaev, I. D., 224
Isaev, Z. I., 626
Tsakova, R. N., 192
Isakova, S., 95
Isfan, E., 77
Ivfari, E., 154
Ishchenko, 0. S . , 315
Ishibashi, N., 174
Ishiguro, M., 403
Ishihara, M., 554
Ishii, Y., 313, 362, 372
Ishikawa, M., 403
Author Index
Isida, T., 381
Iskander, M. F., 408
Ismail, Z. K., 46, 50,
286
Ismailov, M. Z., 625
Ismailzade, I. G., 554
Ismatov, Kh. R., 189
Issleib, K., 498
Ito, T., 415, 541
Itoh, K., 313
Ivakin, A. A., 519
Ivanitskii, V. P., 339
Ivanov, I. A., 61, 65
Ivanov, N. R., 632
Ivanov, S. A., 15
Ivanov, V. I., 355
Ivanov, Yu. A., 351
Ivanova, K. R., 558
Ivanova, N. T., 298
Ivanov-Emin, B. N., 182,
206, 209
Ivanov-Shits, A. K., 584
Ivanovskii, M. N., 6
Ivanyutin, L. A., 358
Iverson, A. A., 307
Ivlev, Yu. N., 315
Ivleva, I. N., 431
Iwamura, K., 11
Iwasaki, H., 414
Iyer, R. K., 552
Izutsu, K., 23
JaCimoviC, L., 184
Jack, K. H., 337
Jacke, A. W., 613
Jacko, M. G., 217
Jackson, N. M., 282
Jackson, R. A., 401
Jackson, W. M., 455
Jacob, A., 608
Jacob, R. A., 304
Jacobi, H., 41
Jacobi, N., 431
Jacobs, H., 47
Jacobs, P. A., 318, 346
Jacobson, R. A., 548, 552
Jacox, M. E., 35, 252,258,
676
Jaffk, H. H., 160
Jagannathan, K. P., 429
Jagur-Grodzinski, J., 499,
65 5
Jahns, H.-J., 442, 497
Jain, B. D., 113
Jain, D. V. S., 307
Jain, P. C., 77
Jain, S. C., 315
JakopEiE, K., 199
James, B. D., 112
James, D. W., 549
Jander, J., 466, 656
Jangg, G., 435
Janin, J., 590, 654

Jannach, R., 290
JanouSek, Z., 108
Jam, G. J., 63, 220, 459
Janzen, A. F., 306, 483.
534, 661, 678
Jarchow, O., 187, 339
Jarke, F. H., 454
Jarosch, J. F., 5
Jarrett, O., jun., 454
Jarvie, J., 242
Jaura, K. L., 307, 315
Jaulmes, S., 203
Jayadevan, N. C., 222
Jaymes, M., 636
Jeanne, G., 558
Jefferson, D. A., 325
Jefferson, R., 501
Jeffery, J. W., 88
JehliEka, V., 132
Jeitschko, W., 158, 409
Jejurkar, C. R., 77
Jeket, K., 494
Jenkins, H. D. B., 44, 49,
610
Jensen, W., 516
Jenson, R. J., 464
Jesson, J. P., 481, 515
Jeung, K. V., 52
Jiang, G. J., 671
Jicha, D. C., 398
Jodhan, A., 295
Joesten, M. D., 497, 498
Johannesson, G. A., 78
Johansson, G., 104, 271,
578
Johansson, L., 222
John, P., 403, 652
Johnson, D. H., 45
Johnson, D. R., 140, 255,
260, 272, 305,446
Johnson, G. K., 50
Johnson, G. R. A., 563
Johnson, H. D., jun., 106,
107, 113
Johnson, K. H., 316
Johnson, R. C., 552
Johnson, S. A., 3, 576, 648
Johnson, S. M., 309
Johnson, V. A, 635
Johnson, W. M., 663
Johnston, H., 458
Johnston, H. S., 463
Johnston, J. H., 326
Johnstone, D., 544
Joklik, J., 297, 298
Jolibois, B., 219
Jolivet, J.-P., 553
Jolly, W. L., 160,242,294,
662
Jonas, A. E., 245, 307
Jones, C. H. W., 394, 636
Author Index
Jones, C. J., 110, 126, 128
Jones, D. E. H., 195
Jones, D. H., 457
Jones, F. T., 95
Jones, J., 472
Jones, L. H., 281
Jones, L. V., 667
Jones, P. R., 273, 564
Jones, R. W., 106
Jones, V. T., 607
Jones, W. E., 651
Jonsson, BO., 287
Joo, W. C., 80, 164, 383
Jordan, A. D., 658
Jordan, R. B., 658
Jordan, S., 452
Jortner, J., 20
Josien, F.-A., 552
Joshi, Y. N., 4
Joslin, T., 651
Jost, K. H., 525, 528
Joubert, J. C., 156, 519
Jourdan, G., 476
Joussot-Dubien, J., 652
Joy, A. D., 185
Joy, C., 591
Joyez, G., 430
Judge, D. L., 266
Jugie, G., 146, 471
Juillet, F., 184
Julean, I., 557
Julian, M. OD., 83
Julien-Pouzol, M., 223
Jull, A. J. T., 225
Jumas, J. C., 51, 584, 586
Jung, K. H., 464
Jungen, G., 272
Junkes, P., 469
Juza, R., 47
Kabachnik, M. I., 501
Kabalkina, S. S., 425
KabrB, S., 223
Kachapina, L. M., 431
Kaczmarczyk, A., 116
KadiE, K., 501
Kadoshnikova, N. V., 209,
629, 630
Kadota, M., 18
Kafalas, J. A., 553
Kaftony, M., 416
Kagan, E. G., 355, 356
Kaidalova, T. A., 307
Kaistha, B. C., 231
Kaitner, B., 542
Kajimoto, O., 282
Kajiwara, M., 508
Kakimoto, M., 257, 272
Kalachev, A. I., 139
Kalder, A., 608
Kalenskaya, A. I., 513
Kalinin, V. N., 133
701
Kalinina, G. S., 133, 388,
402
Kalinina, L. N., 358
Kalitina, L. N , 157
Kalliney, S. Y., 524
Kalnibolotskaya, V. V.,
518
Kaloev, N. I., 69, 557
Kalosh, T. N., 556
Kalra, A. K., 203
Kalsotra, B. L., 113, 217,
21 8
Kamai, G. Kh., 537, 543
Kamarov, V. E., 67
Kamenar, B., 542
Kammula, S., 226, 265
Kampf, A. R., 329
Kamphefner, R. W., 426
Kanamaru, V. F., 96,
Kanchir, E., 187
Kandelwal, J. K., 293
Kanishcheva, A. S., 554,
585
Kanter, M., 89, 578
Kantshev, K., 422,
Kapila, V. P., 518
Kapur, S., 113
Karadakov, B. P., 558
Karaksin, Yu. N., 56, 87,
175
Karapetyan, Yu. A,, 550
Karapetyants, M. Kh., 57,
76, 636
Karataeva, 1. M., 18, 613
Karelin, A. I., 37, 666
Karimov, R. Z., 189
Karlsson, L., 436
Karnaukhov, A. S., 18,
192, 613
Karov, Z. G., 281, 289
Karpov, V. I., 202
Karpov, V. N., 210
Karras, M., 611, 614
Kasai, P. H., 346
Kasatochkin, V. I., 230
Kashima, T., 58
Kashina, N. I., 18, 194
Katagiri, S., 242, 297
Katayama, S., 83
Kato, S., 313, 362, 372,
439
Kato, T., 313
Katrib, A., 595
Katsumata, S., 245, 443
Katyshev, S. F., 71
Kaufman, F., 463
Kaufman, M., 250, 651
Kaulgud, M. V., 491
Kawaguchi, H., 541
Kawaguchi, T., 248, 249
Kawakami, K., 369
Kawami, Y., 353
Kawamura, M., 58
Kawasaki, Y., 364
Kawashima, N., 324
Kay, A. N. L., 82, 174
Kayes, P. J., 285
Kazankova, M. A., 515
Kazantsev, A. V., 133,
495
Kazenas, E. K., 350, 557
Kearns, 0. R., 562
Keat, R., 501, 502, 504
Keeling, G., 392
Keenan, A. G., 441
Keiderling, T. A., 112
Keller, P. C., 141, 147,
170, 534
Kelley, J. M., 360
Kelling, H., 291
Kelly, D. P., 584
Kelsch, U., 529
Kemme, A. A., 361
Kemp, P. J., 102
Kempe, G., 526
Kempny, H. P., 304
Kempter, V., 296
Kendall, D. S., 116,
Kennard, C. H. L., 412
Kennedy, G. J., 652
Kennedy, M. B., 605
Kennedy, R. C., 259, 261,
654
Kennedy, S. W., 440
Kennelly, W. J., 113
Kenney, J. T., 353
Kenjo, T., 459
Keppie, S. A., 393
Kerby, R. C., 10
Kerhelst, R. A., 155
Kerimov, I. G., 648
Kern, R. D., 282
Kerouanton, A., 574
Kerr, D. F., 289, 617
Kerridge, D. El., 64
Kervin, P. W., 228
Kessenikh, A. V., 149
Kessler, Yu. M., 498
Kester, D. R., 611
Kesterke, H. J., 95
Kettle, S. F. A., 392
Kevan, L., 571
Khachatryan, L. A., 184,
617
Khaddar, M. R., 185
Khahlov, Kh. Ya., 625
Khain, V. S., 111
Khan, A. A., 329
Khan, M. M., 536
Khan, V. P., 75
Khanafer, M., 369, 585
Kharakoz, A. E., 36
Khardikova, E. Ya., 68
Kharitonov, N. P., 293
702
Kharitonov, Yu. Ya., 287,
617
Kharitonova, R. I., 413
Kharlamova, E. N., 206
Khatuntsev, G. D., 364
Kheiker, D. M., 632
Khidekel, M. L., 159
Khlebnikov, V. N., 535
Khodadad, P., 369,647
Khodalevich, G. N., 300
Khokhlov, V. A., 65
Khokhlova, G. I., 426
Khomenko, B. S., 202
Khoo, P. H., 408
Khorkov, V. F., 274
Khoshkhoo, H., 260
Khozhainov, Yu. M., 524,
630
Khrameeva, N. P., 542
Khramenko, S. P., 219
Khrapov, V. V., 132, 388
Khudaiberdiev, V. G., 95
Khurana, S. C., 422
Kiang, C. S., 435
Kibblewhite, J. F. J., 324,
566
Kidd, R. G., 306, 392
Kiefer, G. W., 432
Kiess, H., 564
Kietaibl, H., 551
Kiji, J., 424
Kilday, M. V., 669
Kim, B. W., 268
Kim, J. J., 519
Kimbell, G. H., 266, 272,
579
Kimber, B. J., 297
Kimel, S., 252
Kimura, K., 245,443
Kimura, M., 547
Kina, K., 174
Kindeeva, V. P., 413
King, D. A., 270
King, G. H., 147
King, G. W., 261, 620
King, M. G., 96, 188
King, R. B., 144,473
King, T. J., 456, 511
Kinomura, N., 351
Kinoshita, K., 234
Kinsinger, J. A., 560
Kint, S., 570
Kinugasa, M., 669
Kiosse, G. A., 211, 588
Kira, M., 385
Kirby, G. W., 282, 446
Kirby, H. N., 649
Kirchhoff, W. H., 260,446
Kireev, V. V., 508, 509
Kirgintsev, A. N., 279
Kiriyama, H., 405
Kiriyama, R., 405
Author Index
Kiriyanenko, A. A., 5
Kirmse, R., 635
Kirsanov, A. V., 484,493
Kiryakova, I. E.,43, 156
Kisch, H., 432
Kiselev, A. V., 318, 344,
346
Kiselev, Y.M.,678
Kishi, K., 669
Kiso, Y., 292
Kistiakowsky, G.B., 283
Kita, H., 155
Kitaham, K., 405
Kitawaki, R., 526
Kjekshus, A., 459, 468,
532,533, 545,554
Klabunde, K. J., 226
Klaeboe, P., 69
Klanichka, V. M., 426
Klapper, H., 34
Klaska, R., 187, 339
Klassen, J., 141
Klavina, L., 19
Klebanskii, A. L., 388,508
Klein, G. P., 260
Klein, H. A., 495
Klein, W., 551
Kleinberg, S., 418
Kleiss, L. M., 569
Klema, F., 30
Klementeva, I. I., 23
Klemperer, W., 455
Klemm, W., 554
Kleppa, 0.J., 187, 335,
352
Klevtsov, P. V., 209
Klevtsova, R. F.,209
Klier, K., 319
Klimchuk, M. A., 23
Klimek, D. E., 261
Klimenko, A. A., 619
Klimov, A. A., 401
Klimov, V. V., 209, 527
Klingebiez, U., 513
Klingen, T. J., 139
Klingen, W., 531, 635
Klintsov, N. Ya., 64, 68
Klopman, G., 111
Klopsch, A., 492, 558
Klotzbucher, W. E., 433
Klueh, R. L., 2, 7, 8
Klueppel, H. J., 95
Kluge, A., 608
Klyavinya, L. A., 154
Klyuchnikov, V. G., 4
Klyuchnikov, V. M., 181
Klyuchnikova, E. F., 70,71
Klyueva, M. L., 24
Knabe, B., 535
Knachel, H. C., 483
Knehr, H., 453
Kniep, R., 639
Kniga, M. V., 189

Knight, G. C.,668
Knight, L. B., 443
Knisely, A. S., 552
Knobler, C., 643
Knoechez, A., 633
Knoeck, J., 154
Knoll, U.,669
Knole, F., 144
Knop, O., 409, 553
Knowles, D. J., 406
Knox, S. A. R., 395
Knudston, J. T., 591
Knuth, K., 466
Knuth, W., 656
Knyazev, E. A,, 351
Knyazeva, R. N., 638
Knyadeva, N. N., 334
Kobayashi, A., 541
Kobayashi, E., 499
Kobayashi, M., 192, 525,
526
Kober, F., 538
Koch, K., 473
Koch, K.-H., 450
Koch, V. R., 651
Kochergina, L. L., 549
Kocherzhinskii, Yu.A., 429
Kocheskov, K. A., 299,
304,640
Kochi, J. K., 514
Kocova, H., 611
Kohler, H., 501
Koehler, W. H., 437
Konig, K.-H., 521
Koster, H., 314
Kogan, M. J., 656
Kohatsu, I., 413, 559
Kohda, S., 242, 297
Kohl, D. A. 252
Kohl, F. J., 177, 179, 235
Kohle, H. S., 536
Koizumi, M., 96,
Kokotailo, G. T., 529
Kokunov, Yu. V., 656
Kokuvin, N. I., 301
Kolar, D., 557
Kolarov, N., 570
Kolb, J. R., 113
Kolditz, L., 220, 408, 521
Kolenshenko, A. G., 183
Kolerova, E. G., 218
Kolind-Andersen, H., 220
Kolling, 0.W., 24
Kolobova, N. E., 394
Kolodyazhnyi, Yu. V.,
310,394
Kolomiichuk, V. S., 216
Kolosov, E. N., 69
Kolosova, N. B., 88, 438
Kolosova, M. Kh., 211,
219,220
Author Index
Koltsov, S. I., 321
Kolyakova, G. M., 402
Kolyshev, A. N., 297
Kolysheva, V. N., 328
Komalenkova, N. G., 403
Komarova, T. N., 413
Komissarova, L. N., 276,
515, 542, 633
Komiyama, M., 311

Kompa, K. L., 669
Kompanichenko, N. M.,
554, 585
Kon, H., 560

Konaka, S., 547
Kondo, Y.,607
Kondon, T., 240
Kondrashev, Yu. D., 174
Kondratev, S. N., 156,
608, 621
Kondrateva, B. S., 65
Koniger, F., 491
Konishevskaya, G. A., 522
Konnik, E. I., 268
Konoplev, V. N., 112
Konov, A. V., 253, 303,
641
Konstantatos, J., 634

Konysheva, L. P., 408
Koola, J., 367
Kopper, W., 588
Kopylov, E. A., 218
Kopylova, A. G., 36
Kordis, J., 286, 468, 545
Korn, J. K., 224
Kornev, A. N., 351
Kornienko, V. N., 11
Kornuta, P. P., 513
Korobov, M. V., 40
Korolenko, V. G., 628
Korolev, D. F.,277
Korolev, V. K., 303
Korolko, V. V., 508
Korolkov, V. V., 408
Korotaeva, I. M., 315
Korotkevich, I. B., 202
Korovin, S. S., 181
Korpusov, G. V., 102
Korshak, V. V., 139, 230,
508,509
Korshunov, B. G., 641

Kortela, E. K., 611
Kortram, I. E., 499
Kortum, G., 453
Koryakina, N. S., 336
Koryazhkin, V. A., 624
Kosenko, V. A., 171
Koski, W. S., 106, 650
Kosmus, W., 287
Kostanyan, S. T., 184,
617
Koster van Groos, A. F.,

187, 335
703
Kostikov, Yu. P., 580
Kostin, A. P., 19
Kostina, V. G., 493
Kostiner, E., 522
Kostogonov, V. G., 298
Kostyanovsky, R. G., 472
Kostyuchenko, P. I., 231
Kotelnikov, Yu. M., 75
Kotera, Y.,188
Kotina, E. G., 626
Kotlova, A. G., 192
Kotte, B., 501
Koulden, S. A., 104
Kouwenhoven, A. P., 549
Kovacevic, S., 46, 176
Kovachev, T. B., 614
Kovalev, V. V., 303
Kovaleva, I. S., 545, 628
Kovaleva, S. K., 545
Kovalevskaya, I. P., 408
Kovyrzina, V. P., 536
Kozerenko, S. P.,204
Kozhina, I. I., 70, 71, 628
Kozima, S., 381
Kozlov, V. D., 351
Kozlova, N. V., 356, 388
Kozlowski, Z., 17
Kozmin, P. A., 390
Kozmutza, K., 678
Kozub, S. G., 668
Kramer, P. A., 549
Kriimer, V., 212, 547, 559,
585
Kraemer, W. P., 438

Krahe, M., 520,540
Kralichkina, M. G., 544
Kramling, R. W., 256
Krane, J., 29
Kranz, H., 476
Krapukhin, V. V., 350
Krasnobaeva, 0. N.,191
Krasnov, K. S., 40
Krasnov, Yu. N., 357
Krauchenko, L. Kh., 630
Krause, P. F., 450
Krause, R. F., jun., 194,
67 1
Krauss, D., 551

Kravchenko, E. A., 308
Kravchenko, M. S., 59
Kravchenko, 0. V., 111,
112, 176
Kravtsov, D. N., 306

Krebs, B., 51, 168, 369,
370, 484, 585, 599, 605,
623, 641, 642
Krenev, V. A., 103, 150,
482
Kresge, A. J., 670
Kreshkov, A. P., 100
Krespan, C. G., 613
Kress, J., 439
Krestov, G. A., 23
Krestovnikov, A. N., 73
Kreutsis, R. P., 427
Kriegsman, H., 306
Krischner, H., 58
Krisher, L. C., 296
Krishnamachari, N., 524
Krishnamurthy, S., 160
Krishnamurthy, S. S., 147,
506
Krishnan, C. V., 13
Krishnan, R. S., 264, 629
Kristiansen, E. S. S., 626
Kristoff, J. S., 185
Krivovyazov, E. L., 526,
527
Krivtsov, N. V., 43, 57,

150, 154
Krivy, I., 613

Kfii, O., 177
Krizhanovskii, A. V., 18
Krogh-Moe, J., 43, 53, 66,
156, 197
Krogmann, K., 73, 173

Kroll, J. A., 143,
Kroll, M., 151
Kropshofer, H., 153, 357,
643
Kroth, H. J., 372,

Kroto, H. W., 261
Kruchenko, V. P., 613
Kruchna, O., 298
Kruck, T., 97,444
Kruczynski, L. J., 537
Krueger, J. H., 667
Kruglaya, 0. A., 133,402,
388
Kruglik, A. I., 629

Krumgalz, B. S., 15, 23,
24
Krusic, P. J., 514

Kruss, B., 551
Kruzlyak, Yu. A., 14
Krylov, V. S., 351
Krysov, V. V., 517
Kryukova, V. N., 79, 351
Ksenzenko, V. I., 641,
642
Ku, R., 270

Kubasov, A. A., 346
Kubasov, V. L., 50
Kubasova, L. V., 158
Kubo, R., 19
Kubrak, Yu. P., 66
Kucera, G. H., 3, 624
Kuchen, W., 473, 479,
544
Kucherov, P. V., 427

Kuchkina, E. D., 83
Kuckertz, H., 374
Kuczkowski, R. L.,247
Kudish, A. I., 519
704
Kudryashov, N. S., 408
Kudryavtsev, N. T., 524
Kudryavtsev, Yu. P., 230
Kudryavtseva, T. F., 257
Kuehnlenz, G., 160
Kummel, R., 441,461
Kiindig, E. P., 432, 433
Kueppers, H., 34
Kiippers, J., 270
Kukaich, S. G., 247
Kukis, L. M., 61
Kukolich, S. G., 257, 261
Kukulieva, E. I., 289
Kulba, F. Ya., 200, 215,
218
Kulikov, A. I., 336
Kulilov, L. N., 662
Kulikovskaya, N. P., 344
Kulkarni, V. H., 312
Kumada, M., 292,403
Kumar, N., 217, 218
Kumar, S., 100
Kumar Das, V. G., 313
Kummer, D., 314
Kumok, V. N., 203
Kunchuliya, E. D., 649
Kunin, L. L., 3, 6
Kunte, N. S., 636
Kunz, A. B., 242,297
Kunze, E., 364, 365
Kunze, J. 408
Kunze, U., 367
Kupcik, V., 638
Kura, G., 525
Kuramshin, 1. Ya., 309
Kurbatov, G. M., 183
Kurbatov, N. N., 71
Kurchyumov, G. M., 197
Kurdyumov, A. V., 228
Kureishi, A. W., 457
Kuribayashi, S., 167
Kurina, L. N., 257
Kuriyama, K., 11
Kurlova, T. V., 355
Kurlyandskaya, I. I., 257
Kurokawa, Y., 461
Kuropatova, A. A., 197
Kuroya, H., 541
Kursanov, D. N., 315
Kusov, Yu. I., 537
Kustin, K., 655
Kutek, F., 43
Kutoglu, A., 572
Kutzelnigg, W., 104
Kuvakin, M. A., 68, 69,
194
Kuwabara, T., 199
Kuzma, Yu. B., 173
Kuzmenko, N. M., 344,
346
Kuzmenkov, M. I., 520
Kuzmin, K. I., 535
Author Index
Kuzmin, 0.V., 303
Kuzmin, R. N., 545
Kuzmina, I. P., 352
Kuzmina, L. G., 357
Kuznetsov, A. A., 303
Kuznetsov, A. F., 101
Kuznetsov, B. P., 619
Kuznetsov, L. V., 584
Kuznetsov, P. N., 289
Kuznetsov, S. I., 53
Kuznetsov, V. A., 50, 75,
325, 336
Kuznetsov, V. G., 43, 57,
390,528, 585
Kuznetsov. V. 1.. 209
Kuznetsova, A. -G., 19,
355
Kuznetsova, L. V., 52
Kvashina, E. F., 431
Kvitek, V., 59
Kwan, C. T., 140
Kwan, T., 611
Kwang, A. F., 207
Kydon, D. W., 658
Kyskin, V. I., 137
Kyuntsel, I. A., 503
Laane, J., 567
Labarthe, J.-C., 523
Labarre, J.-F., 142, 143,
145, 147, 148, 152, 439,
443,481, 506
Labarre, M.-C., 439, 493,
497
Lacaze, P.-C., 662
Lacoste, G., 452
Laugt, M., 522, 527, 528
Laffitte, M., 224, 648
Lafon, E. E., 228
Lafont, R., 184
Lagodzinskaya, G. V., 159
Lagow, R. J., 133,148,226,
238, 654
Lagow, R. L., 304
Lagowski, 3. J., 20, 162,
437
Lagrange, P., 52, 240
Lagrange, P., 53, 240
Lal, S., 422
Lam, D. K., 238
Lamanova, I. A., 535, 540
Lamb, J. D., 253
Lambert, C., 272, 579
Lambert, L., 159, 266
Lamotte, B., 541
Lampe, F. W., 296, 453
Lancucki, C. J., 609
Land, J. E., 565
Landa, B., 677, 679
Lang, J., 48, 88, 200, 427,
468
Langer, D. W., 78
Langer, K., 339

Langford, C. H., 656
Langford, R. B., 272, 575
Lapitskaya, E. V., 101
Lapko, K. N., 192,520
La Placa, S. J., 112
Lappert, M. F., 147, 373,
393, 421,424
Lapshin, V. A., 16, 611
Laptev, V. T., 121
Larin, A. A., 238
Larinova, T. N., 213
Larkin, R. H., 486
Larsen, F. K., 157
Larson, R. W., 346
Larsson, L. O., 52, 615
Larsson, R., 220, 614
Larvelle, P., 203
Lasalandra, L., 16
Laskar, A. L., 54
Lasne, C., 9
Lassettre, E. N., 243, 246
Lisztity, S., 207, 215
Latrous, H., 16
Latscha, H. P., 495, 496,
55 1
Latyaeva, V. N., 389

Lau, C., 621
Lauca, C. D., 607
Laue, H. A. H., 666
Laughlin, D., 407
Laulicht, I., 248
Launay. G., 662
Laurent, J.-P., 146,
177, 471, 538
Laurent, Y., 48
Laussac, J.-P., 146, 77,
47 1
Lavalley, J. C., 248
Lavendy, H., 192
Lavilla, R. E., 246
Lavrenteva, E. A., 159
Lavrov, A. V., 521
Lavrukhin, B. D., 355
Lawesson, S.-D., 220
Lawrence, G.-M., 272
Lawrence, N. C., 541
Lawton, E. A., 659
Lawton, S. L., 529, 552
Layten, S. W., 138
Lazarev, V. B., 49, 354,
554,585, 628
Lazarini, F., 557
Lazennec, Y.,
9
Leach, H. F., 344
Leadbetter, A. J., 317
Leary, K., 679, 681
Leary, R. D., 485, 489
Lebedev, V. I., 225, 315
Lebedeva, L. I., 518
Leboshchina, V. I., 83
Lebreton, J., 151
Author Index
Le Brusq, H., 574,584
Le Carpentier, J.-M., 551
Lecorre, C., 426
Ledesert, M., 34
Ledesert, M.-A., 92
Le Duff,Y., 430
Lee, A. G., 219
Lee,J. D., 39
Lee, L. C., 266
Lee, P. L., 81
Lee, R. H., 8
Lee, S. T., 265
Leech, J. W., 272
Lee-Ruff, E., 434, 657
Lefebvre, J., 553
Lefebvre-Brion, H., 454,
514
Lefehocz, J. F., 312
Lefevre, H., 45
Lefevre, R. J. W., 142
Leffert, C. B., 455
Legasov, V. A., 302, 678
Legendre, B., 370,426,
429
LCger, J.-M., 198
Legeta, L. V., 212
LeGeyt, M. R., 474
Leggett, T. L., 252
Legon, A. C., 643
Legrand, P., 56, 608
Lehmann, H.-A., 157,
501, 522,608
Lehmann, M. S., 637, 674
Lehn, J. M., 27
Le Holding, A. F., 392
Leibovia, C., 439
Leibovici, C., 142, 143,
145, 147, 148, 152,443,
481, 567
Leitch, D. M., 292
Leites, L. A., 137
Leith, I. R., 344
Leitzke, O., 153
Lelieur, J. P., 20
Lemaire, J., 247
Lemerle, J., 553
Lemley, A. T., 437
Lemont, S., 13
Lenglet, M., 202
Lenhert, P. G., 498
Leonhardt, G., 573
Leonteva, I. A., 157,
409
Leoscher, B. R., 431
Lepeshkov, 1. N., 18,
191, 289,461, 613
Lequan, R.-M., 494
Le ROUX,H. J., 208
Leroux, P., 307
Leroy, M. J. F., 547
Leshchenko, A. U., 201
Lesigne, B., 617, 666
705
Lessard, C. R., 261
Lester, J. E., 39
Letoffe, J.-M., 55, 578
Lett, R. G., 268
Leung, K., 335
Leung, K. Y., 542
Leung, P. S., 15
Leutwein, F., 239
Levasseur, A., 87, 158
Levchishina, T. F., 307
Levin, A. A., 256
Levin, I. S., 216
Levin, I. W., 250
Levin, V. P., 253
Levine, C., 9
Levitt, B. P., 285
Levy, B., 438
Levy, D. H., 282
Levy, H. A., 14
Levy, J. B., 259
Lew, W. Y. W., 616
Leyte, J. C., 247
Llabador, Y.,315
Llonch, J. P., 367
Lloyd, D. J., 87, 158,
276
Lloyd, D. R., 150, 307,
608,650,660
Li, W.-K., 679
Li, Y. S., 142, 145, 296,
305, 383,470,491
Libbey, E. T., 307, 394
Libich, S., 422
Libowitz, G. G., 45
Liddiard, V. C., 449
Lide, D. R., 255, 305
Liebau, F., 526
Liebertz, J., 210
Liebhafsky, H. A., 567
Liebmann, J. F., 678
Lien, W. S., 534
Liengme, B. V., 313
Liepina, L., 176
Lietzke, O., 643
Lifshitz, C., 274
Likforman, A., 212
Likhanskaya, N. V., 100
Lillebuen, B., 66
Liminga, R., 56
Limingen, R., 631
Lin, C.-L., 244
Lin, M. C., 665
Lin, S. B., 337
Lin, S.-M., 250
Lin, T. P., 506, 513
Lin, T. S., 148
Lincoln, S. F., 205,541
Lind, M. D., 427, 660
Lindahl, C. B., 659
Lindheimer, A., 23
Lindholm, E., 287
Lindemann, H., 308
Lindley, P. F., 88
Lindner, E., 186, 366,
367, 492
Lindqvist, O., 629, 636
637, 638, 674
Lindsey, D. C., 606
Lines, E. L., 145, 481,
485, 501
Linke, K. H., 96, 97, 444
Lipka, I., 352
Lippard, S. J., 112
Lippincott, E. R., 308,
618
Lippmann, F. J., 626
Lipscomb, W. N., 105,
113, 116, 121, 124, 133
Lischewski, M., 498
Lisitsa, M. P., 582
Liskow, D. H., 257, 676
Lisle, J. B., 163
Lissi, E. A., 268
Lister, D. G., 245, 255
Lister, M. W., 605
Litchman, W. M., 438
Little, D. J., 634
Little, L. H., 270, 320
Little, T. E., 2
Littlefield, L. B., 489
Litvin, B. N., 351
Litvin, Yu. A., 227
Litvincheva, A. S., 458
Litvinov, Yu. G., 461
Litvinova, G. V., 83
Litvinova, T. I., 193
Liu, B. 676
Liu, C. L.,274, 607
Liu, C. S., 404
Livadko, L. V., 199
Lobachev, A. N., 325,
336, 352, 554, 644
Lobacheva, M. P., 76
Lobanok, A. N., 192,
520
Lobanov, 0. P., 513
Lobkovskii, E. B., 112,
180
Lobusevich, N. P., 298
Lockhart, J. C., 143
Lockman, B., 121
Lockwood, D. J., 459
Lodzinska, A., 499
Lons, J., 479
Lofstrand, B., 73
Logan, N., 457
Logvinenko, V. A., 84
Lok, M.T., 21
Lokshin, B. V., 315, 394
Lokutsievskii, V. A., 318
Lomakova, I. V., 185,
357
Long, J., 532
Longeri, M., 655
706
Longhi, P., 16
Longoor, F., 167
Loos, K. R., 189
Lopitaux, J., 202
Lopusinskii, A., 530
Lorca, E., 208
Lord, R. C., 265
Lorenz, R., 599
b r i e r s , J., 327
Loriers-Susse, C., 327
Lorthioir, G., 237
Lory, E. R., 140
Loseva, G. K., 18
Loshkareva, N. I., 101
Lott, J. W., 114, 115
Lovas, F. J., 140
Love, R. A., 137
Low, M. J. D., 81
Lowe, B. M., 438
Lowman, D. W., 105,
106
Lowndes, R. P., 224
Lozach, A. M., 89,206,
625
Lu, M. F., 55
Lucchesi, C. A., 39
Lucken, E. A. C., 550
Luds, K. R., 341
Ludwig, A. C., 574
Luger, P., 602, 606
Lugin, V. N., 554,585
Lugo, R., 20
Lukas, J., 543
Lukaszewicz, K., 77
Lumsford, J. H., 567
Lundgren, J. O., 617
Lundin, R. E., 371
Lundner, P., 104
Lundstrom, T., 4,78, 171
Lunsford, J. H., 344, 346,
562
Lupton, M. K., 494
Lust, L. F., 5
Lustig, M., 490, 552, 662
Lutseako, I. F., 515
Lutz, H. D., 95, 574
Luz, Z., 15
Luzganova, M. A., 298
Luzhnaya, N. P., 216,
5 87
Lyakhovitskaya, V. A.,
584
Lyapina, S. S., 201
Lygin, V. I., 274, 318,
344,346
Lyman, J. L., 464
Lynaugh, N., 150
Lynch, A. W., 226,228
Lynton, H., 307
Lysenko, Yu. A., 197
Lyskova, Yu. B., 648
Lyssandtrae, N., 645
Author Index
Lyubarskii, G. D., 274
iyubutin, I. S., 352
Lyudviov, R. B., 429
Maartmann-Moe, K.,
645
Maass, G., 250, 405
McAdam, A., 525
MacAlister, S. P., 12
McAloon, B. J., 161, 516
McAloon, K. T., 555
McAloon, K. T., 555
McAuley, J. H., 252
Macauly, R., 284
Macbeath, M. E., 162
McBride, D. W., 537
McCarthy, D. J., 235,
607
McClung, R. E. D., 243
McColm, I. J., 237
MacCordick, J., 75, 284,
658
McCracken, G. M., 2
McCullough, J. D., 643
McCullough, J. J., 477
McCullough, R. D., 246
MacDiarmid, A. G., 314,
395
MacDonald, A. L., 600
McDonald, J. R., 147,
460
Macdonald, N. S., 207
MacDougall, J. K., 398
McDowell, C. A., 200,
265, 592, 595
McEwen, W. E., 546
MacFadden, K. O., 464,
465
McFarlane, H. C. E.,
474
McFarlane, W., 103, 474,
620
McGee, H. A. jun., 140,
462
McGlinchey, M. J., 226
McGlynn, S. P., 147, 460
McGraw, R. K., 406
McGregor, A., 398
McGuire, G. E., 271, 579
McGurk, J., 265
McGurk, J. C., 284
Mach, K., 363
Machatek, J., 175
Machavariani, Z. N., 352
Machmer, P., 196
Machova, J., 363
Maciejko, J. J., 450
Mack, D. P., 512
Mack, G. P. R., 261
Mackay, K. M., 389
McKay, V., 431
McKean, D. C ,246,247
McKee, D. E., 549, 661,

677, 678
UcKenney, R. L., 600
Uackenzie, J. D., 224
vlackenzie, R. E., 178
UcLaughlin, E., 107
McLaughlin, G. M., 180,
315
McLay, D. B., 247
McLean, P. R., 620
McLean, R. A. N., 297,
595
McMeeking, J., 379
MacMullin, E. C., 372
MacNamee, R. W., 443,
473
McNeill, E. A., 119
McNichol, B. D., 189,
341
Maddock, A. G., 516,
631
Maddon, H. H., 270
Maeda, H., 353
Maeda, K., 292
Maekawa, T., 628
Maervoet, G., 533
Mages, G., 557
Maggio, F., 367
Magmedov, G. K. I., 392
Magunov, R. L., 351,
408
Mahajan, 0.P., 231
Mahajan, V. K., 357
Maheshwari, R. C., 537
Mahieu, J. M., 192
Mahler, W., 514
Mahlman, H. A., 458
Mahmood, A. J., 516
Maier, L., 476, 477, 478,
487
Maijs, L., 77
Mainwaring, D. E., 340,
34 1
Maiorga, E. K., 350
Maiorova, L. I?., 402
Maitra, A. N., 165
Makarevskii, V. M., 19
Makariunas, K., 636
Makaruk, M. S., 491
Makashev, Yu. A., 2 15
Makatum, V. N., 570
Makhalkina, V. L., 300
Makhmetov, M. Zh., 581
Maki, A. G., 272, 608
Makide, Y., 236
Makitra, R. G.,491
Makolkin, I. A., 289
Makordei, F. V., 43
Maksimenko, A. A., 19,
191, 192,613
Maksimenko, S. G., 537
Maksimov, B. A., 351
Author Index
Maksimova, S. I., 43
Maksina, N. V., 68
Maksyutin, Yu. A., 308
Mazaman, B., 425
Malaspina, L., 10, 546
MaleSiC, M., 557
Malhotra, K. C., 365,
589, 617, 621, 622, 636
Malhotra, M. L., 449
Malik, A. U., 536
Malikova, E. D., 3, 6
Malinovsky, M., 193
Malinausakas, A. P., 67
Malkova, G. Ya., 389
Malkova, T. V., 187
Mallinson, P. R., 25, 164,
246,472
Malm, D. A., 272
Malm, J. G., 681
Malmberg, M. S., 248
Malov, Yu. I., 668
Malova, N. S., 215
Maltsev, A. A., 58, 624
Maltsev, A. K., 250
Maltsev, V. T., 336, 352
Maltseva, N. S., 60
Malygin, A. A., 321
Malykhina, I. G., 515
Mamakov, K. A., 543
Mamantov, G., 546
Mamedov, K. K., 648
Mamedov, K. P., 619
Mamedov, Kh. S., 157
Manakov, V. M., 336
Manca, P., 207
Mancini, C., 59
Mandelman, M., 453
Mandt, J., 168
Maneglier-Lacordaire, S .,
369, 647
Manerva, M., 570

Manewa, M., 41, 149,
413, 629
Manhas, B. S., 536

Manis, P. M., 247
Manley, T. R., 505
Mann, A. W., 522
Mann, G., 178
Mann, R. H., 247
Manne, R., 245
Manning, A. R., 393
ManojloviE-Muir, Lj.,
504
Manolatos, S., 58
Manor, S., 458, 672
Manoussakis, G. E., 544
Manvelyan, M. G., 18
Maouche, B., 161
Mar, R. W., 103, 173,
174
Maraine-Giroux, C., 155

Marandiuc, D., 557
707
Marchand, A., 232
Marchand, R., 88,200,
220,468
Marchenko, V. N., 310

Marchenkova, N. G., 678
Marchese, F. T., 674
Marcotte, R. E., 251
Mardaleishvili, R. E.,
232
Mardirosova, 1. V., 524

Maresch, G., 303
Margerum, D. W., 652
Margineanu, F.,444
Margrave, J. L.,4, 46,
50, 133, 193, 250, 307,
403,405, 654
Maria, H. J., 147, 460
Mariezcurrena, R. A., 33,
154
Mariggele, E., 303
Marin, A., 8, 560
Marinin, A. S., 302, 678
Marinkovic, S., 236,468
Marketz, H., 291
Markham, R. T., 472
Markov, B. F., 65, 68
Markovich, I. S., 59
Markovskii, L.N., 484
Markovskii, L. Ya., 174
Marks, T. J., 113, 393
Marmet, P., 431
Marner, F. J., 95
Marnry, K., 616, 646
Maroni, V. A., 2
Marosi, L., 307, 441
Marquarding, D., 516
Marr, D. H., 507
Marriott, R. C., 469
Marseglia, E. A., 44, 308
Marsh, H., 232
Marsh, P., 230
Marsh, W. C., 511
Marsmann, H., 469
Marson, R., 605
Martin, C.,526
Martin, D. R., 472, 495
Martin, J. J. P., 413
Martin, J. S., 17
Martin, R. B., 579
Martin, R. P., 607
Martinez-Ripoll, M., 94
545
Martin-Lefevre, C., 413
Martschei, L., 539
Martynenko, B. V., 522
Martynenko, L.I., 678
Martynov, B. I., 402
Marumo, F., 541
Marusin, V. V., 297
Maryanoff, B. E., 581
Marynick, D. S., 113,
121, 124
Maryott, A. A., 248

Marzocchi, M. P., 257
Masanet, J., 435
Mascherpa, G., 149, 458
Mascherpa-Corral, D.,
206
Mashchenko, V. M., 321

Mashkov, S. A., 559, 628
Masimov, E. A., 648
Maslennikov, V. P., 517
Mason, G. W., 517
Masri, F. N., 254
Massa, L. J., 675
Masse, R., 326, 328,
525
Massies, J.-C. 212

Massion, P. J., 335
Massol, M., 418
Masson, C. R., 325, 338
Massonne, J., 176
Massucci, M. A., 521
Mastropaolo, D., 414
Mastryukov, V. S., 121
Masukane, K., 483
Mather, G. G., 315
Mathew, M., 120
Mathiev, J.-C., 427
MatiaSovskjr, K., 193,
194
Matochkin, U. S., 139

Matray, C., 590, 654
Matskvich, E. S., 231
Matsubayashi, G. E., 312
Matsuda, O., 191
Matsumoto, K., 541
Matsumoto, M., 249
Matsuo, T., 192, 525
Matsuura, H., 246
Matsuzaki, I., 567
Matsuzaki, R., 557
Matsuzaki, T., 611
Mattes, R., 479
Matteson, D. S., 1.17
Matthew, J. A. D., 80
Matthews, R. W., 458
Matvienko, V. G., 40
Matyash, V. I., 339
Maul, W., 649
Mauras, H., 441
Maurin, M., 74, 475,
519, 612, 613
Maus, E., 588

Mavani, I. O., 77
Mavridis, R. P., 461,
613
Maxwell, J. R., 225

May, N., 96
Maya, W., 659
Mayer, E., 141, 146, 164,
472
Mayer, H., 365, 521, 527

Mayer, U., 499
708
Mayerle, J. J., 112
Mayet, J., 45, 46, 176
Mayhan, K. G., 358
Maylor, R., 614
Mays, R., 163
Mazac, C. J., 295
Mazalov, L. N., 271, 606
Mazeau, J., 430
Mazepova, V. I., 57, 636
Mazurier, A., 369
Mazykin, V. V., 575
Mazzola, E., 372
Mazzucato, U., 655
Meads, R. E., 188,409
Meakin, P., 282, 481,
515
Mechkouskii, L.A., 429
Median, A. S., 521
Medvedeva, Z. S.,545,
628
Meek, D. W., 406
Meerts, W. L., 454
Meguro, K., 324
Mehdra, S. K., 169
Mehrotra, A., 185
Mehrotra, M. L., 219
Mehrotra, R. N., 261
Mehrotra, S. K., 357
Mehrotra. R. C., 169,
185, 357, 360, 361, 526
Mehta, 0. P., 65
Meier, W. M., 189
Meikle, G. D., 490
Meinert, H., 657
Meinzer, A. L., 105
Meir, W. M., 341
Meirer, A. J., 272
Meirman, S., 248
Meisel, A., 573
Meisel, M., 302, 493
Meiser, P., 446
Mekhtiev, M. I., 648
Melchenko, G. G., 353
Melcher, L. A., 142, 162
Melekh, B. T., 155, 580
Meller, A., 165, 303
Mellman, T. M., 258
Melnik, M. T., 188
Melnikov, P. P., 515
Melnikov, Yu. T., 408
Melnikova, R. Ya., 621
Melnikova, S. I., 156,
608
Melton, C. E., 571
Menchetti, S., 186
Mendelsohn, M. H., 602
Mendes, E., 360
Menke, H., 382,469
Mentzen, B., 265
Merbach, A., 492
Mercer, G. D., 127
Mercurio, J. P., 171
Author Index
Mereiter, K., 191
Mering, J., 238
Merkel, P. B., 562
Merkulova, K. S., 18
Merlet, P., 439
Merlino, S., 157, 331,
337
Merriam, J. S.,164
Meshkova, S., 100
Mesmer, R. E., 149
Mktrot, A., 53, 239, 240
Mettee, H. D., 281
Metz, B., 28, 98, 99,
41 8
Meunier, A., 438
Meunier, G., 644
Mews, R., 538, 592, 596
613
Meyer, B., 573
Meyer, J. A, 281
Meyer, R. T., 226,228
Meyer, T. J., 398
Meyer, W., 242
Meyers, E. A., 548
Meyerson, S., 565
Mezakovskii, L. A., 427
Meznik, L., 519
Mialocq, J. C., 666
Michael, J. U., 267
Michalski, J., 528, 530,
531
Michejda, C. J., 434
Michel, A., 353
Michel, C., 219, 554
Michels, W. C., 409
Mickey, C. D., 531, 627
Michoulier, J., 328
Middleton, R., 452
Middleton, T. B., 487
Mielcarek, J. L., 170
Mievich, E. G., 288
Miftakhova, R. G., 533,
537
Migliorini, M. G., 257
Mihichuk, L., 534
Mikhaiel, S.A., 194
Mikhailova, E. M., 18,
667
Mikhailyuk, Yu. I., 203
Mikhaleva, T. G., 189
Mikhaylova, V., 174
Mikheev, E. A., 298
Mikheeva, L. M., 200,
205
Mikheeva, V. I., 18, 92,
112, 195
Mikler, J., 314
Mikolajczyk, M., 477
Mikovsky, M. A., 193
Mikuni, H., 258,445
Milaev, S. M., 100
Milchereit, A., 182
Mile, B., 245

Milionis, C. C., 265
Millard, M. M., 371
Millberg, M. E., 155
Mille, G., 371
Miller, C. E., 40
Miller, F. A., 482
Miller, G. A., 360
Miller, J. L., 371, 486
Miller, J. M., 141
Miller, K., 425
Miller, L. L., 651
Miller, P. T., 498
Miller, T. A., 560
Miller, V. R., 114, 120,
123, 142
Milligan, D. E., 35, 252,
258, 676
Millington, D., 510, 511
Mills, H. H., 502
Mills, I. M., 472, 608
Mills, J. F., 659
Mims, C. A., 250
Minano, A. S.,64
Minchenko, V. I., 67
Minck, R. W., 9
Mines, G. W., 261
Minnhagen, L., 4, 78
Mironenko, A. P., 662
Mironov, K. E., 271,
468, 579
Mironov, V. E., 224,
334, 556
Mironov, V. F., 133, 299,
300, 364, 386,497
Mironova, Z. N., 219
Mirri, A. M., 255
Mirskov, R. G., 315
Mishchenko, K. P., 13,
24
Mishchenko, Yu. A., 274
Mishenov, Yu. M., 88,
438
Mishra, A., 449
Mishra, S. P., 487, 504
Miskiv, M. G., 427
Mislow, K., 581
Misra, S., 216
Mitchell, P. D., 306
Mitoff, S. P., 9
Mitomo, N., 570
Mitschke, K.-H., 489
Mitschler, A., 526
Mitsyuk, B. M., 322
Miura, M., 274
Mizuguchi, J., 570
Mizukusa, S., 79
Mizuta, M., 313, 362,
372
Mizuta, S., 41
Mo, Y.K., 111
Mochalov, K. N., 621
Author Index
Mocek, K., 97, 612,
615
Mochel, A. R., 256
Modro, T. A., 516
Moedritzer, K., 479
Msller, J., 540
Moller, K. D., 288
Moeller, M. B., 147, 493
Moeller, T., 507
Moffat, J. B., 139
Mogi, I., 526
Mohan, N., 151, 278,
531, 626
Mohana Rao, J. K., 631
Mohhen, V. A., 435
Mohtachemi, R., 372
Moiseendo, S. S., 649
Mokhosoev, M. V., 192,
202,210
Molchanova, 0. P., 44
Molinie, P., 179
Molochko, V. A., 197
Molodkin, A. K., 19,
61 3
Molodtsov, S. S., 535,
536
Mondegarian, R., 202
Montel, G., 523
Montle, J. F., 358
Moodenbaugh, A. R., 95
Moody, D. C., 106, 109
Moody, S. S., 263
Moore, C. B., 261
Moore, C. F., 4
Moore, G. S. M., 317
Moore, J. E., 187
Moore, P. B., 87, 156
Moore, P. L., 273
Mootz, D., 639
Morachevskii, A. G., 11,
12, 13
Moras, O., 28, 98,99
Morassi, R., 673
Moravec, J., 613
Mordovin, A. E., 68
Moreau, J. J. E., 291
Moreland, C. G., 167,
489
Moret, J., 49, 636, 637,
638
Moret-Bailly, .I.243
,
Moretto, H., 292, 377
Morgan, W. E., 39,424,
546
Mori, Y.,561
Moriarty, J. A., 86
Morillon-Chapey, M.,
246
Morley, C., 266,273
Moro-oka, Y.,423
Morosin, B., 425
Morozov, A. I., 43, 289
709
Morozov, E. V., 40
Morozov, V. A., 6
Morozova, L. V., 392
Morozova, T. V., 290
Morrell, B. K., 677
Morris, A., 456
Morris, D. L., 549
Morris, E. D., jun., 458
Morrison, J. D., 243,
297,436, 589
Morrison, R. T. W., 409
Morrison, W. H., 286,
460
Morrow, B. A., 318
Morrow, R., 4
Morse, J. G., 143, 145,
480,538
Morse, K. W., 143, 538
Mortland, M. M., 332,
333
Morton, J. R., 591
Moruga, L. G., 157
Mosanski, J., 619
Mosbo, J. A., 498, 516
Moser, W., 405, 41 2
Moser, Z., 427
Moshinski, A. J., 612
Moshinskii, A. S., 191,
203, 613
Moskovits, M., 432, 433
Moskovtsev, V. V., 298
Motooka, I., 192, 525,
526
Motornaya, G. A., 422
Motoyama, M., 18
Motte, J. P., 47, 48, 88,
444
Mougin, J., 651
Moule, D. C., 261
Movius, W. G., 311
Mozer, T. J., 522
Mozharova, T. V., 19
Muchizuki, A., 276
Miiller, A., 151, 278,
53 1
Miiller, B., 194
Miiller, D., 223
Miiller, F., 352
Muller, J., 144
Miiller, P., 398
Miiller, R., 242, 297,
383
Miiller, U., 54, 55, 447,
449, 551
Mueller, W., 11, 96
Muller-Buschbaum, H., 88,
93, 202, 210, 219
Muetterties, E. L,186,481,
515
Muir, K. W., 504
Mukad, E., 267
Mukaibo, T., 197, 241
Mukherjee, A. D., 554

Mukherjee, D. C., 539
Mukerjee, K. P., 427
Mukherjee, R. N., 529
Mukmenev, E. T., 508
Mullen, D. J. E., 543
Mullen, P. A., 460
Muller, A., 491, 626,
628
Muller, D., 625, 648
Muller, J. H., 24
Multani, R. K., 113, 217,
218
Mumme, W. G., 55, 610
Munir, Z. A., 207
Munshi, K. N., 210
Murata, A., 100
Murata, H., 296
Muratova, A. A., 309
Muraveva, G. A., 613
Muravev, I. V., 529
Murgulescu, I. G., 244
Murken, G., 409
Murphy, D. W., 389
Murphy, J. L., 365
Murray, J. J., 532
Murray, M., 490, 504
Murthy, A. R. V., 176,
530
Musgrave, T. R., 148
Musher, J. I., 482
Mussini, T., 16
Mustya, I. G., 211, 588
Musulin, B., 656
Muthukrishnan, L., 263
Mutin, J. C., 570
Muzalov, L. N., 579
Myakishev, K. G., 19
Nabika, K., 381
Naccache, C., 271, 324,
346, 566
Nachbaur, E., 48, 287,
609
Nadis, J. A., 26
Nadkarni, R. A., 216
Nagai, S. 318, 575
Nagai, T., 93
Nagarajan, G., 491
Nagashirna, K., 276
Nagatini, M., 19
Nagorskaya, N. D., 78
Naik, D. V., 383
Naik, R. K., 261
Nair, C. G. R., 442
Nakabayashi, T., 9
Nakagawa, T., 246
Nakamura, M., 100
Nakamura, O., 405
Nakamura, S., 60
Nakao, R., 530
Nakatani, M., 153
Author Index
710
Nakayama, M., 461
Nakayama, N., 79
Nakumara, N., 483
Nambisan, P. N. K., 442
Nametkin, N. S., 303
Nanes, R., 607
Napoli, A., 422
Narayanan, P. S., 632
Nardin, G., 369
Narten, A. H., 14
Narula, S . P., 357
Nasirov, V. I., 459
Naslain, R., 171
Nasonov, Yu. V., 67
Naumann, D., 33, 591,
660
Naumov, V. A., 485, 491
Naumova, N. N., 303
Naumova, T. N., 595
Nave, C., 29
Navratil, J. D., 276
Nawata, Y., 29
Nayar, V. V., 473
Nazarov, A. S., 240
Nazarova, 1. N., 315
Nazery, M ., 169
Neal, H. G., 603
Nechstein, J., 320
Neef, H., 383
Nefedov, V. I., 76, 656
Negita, H., 197, 215
Negrebetskii, V. V., 149,
159
Neilson, R. H., 144, 374
Nekrasov, L. I., 563
Nelander, B.,654, 655
Nelson, N. J., 185
Nelson, P. A., 6
Nenno, E. S., 18
Nereson, N. G., 237
Neronova, N. N., 84
Nesmeyanov, A. N.,408
Nesternenko, V. I., 554
Neto, N., 249
Netzer, A., 670
Nevolina, N. A., 16
Newlands, M.J., 394
Newman, A. R., 393
Newman, G. A., 152,
57 1
Newman, K. E., 154
Newman, R. N., 36
Ng, C.-Y., 679
Ng, H. N., 461
Ng, T. L., 265
Nguen Ngok Kuan, 71
Nguen Van Chen, 518
Nibler, T. W., 444
Nichkov, I. F., 68,408
Nicholls, C. J., 82, 174
Nicholls, R. W., 434
Nichols, J. M., 529
Nichols, M. C., 174

Nicholson, A. J. C., 406
Nicholson, B. K., 390
Nicholson, D. A., 477,
478
Nicholson, D. G., 410,
545,554
Nicolini, M., 399
Nicotera, E., 648
Niecke, E., 377, 494,
5 06
Niedenzu, K., 142, 150,
164, 165, 166, 167,
388, 503
Nielsen, N., 678
Niemann, D., 470
Nietsche, H., 4
Niihara, K., 171, 173
Niinisto, L., 52, 615
Nijman-Meester, M. A.
M., 662
Niki, H., 267, 458, 463
Nikiferova, E. M., 227
Nikitin, B. M., 193
Nikitin, I. V., 567, 665
Nikitina, M. P., 317
Nikitina, Z. K., 549, 666
Nikolaev, N. S., 661
Nikolaev, R. K., 183
Nikolaeva, N. K., 272
Nikolenko, L. N., 678
Nikolina, V. Ya., 344
Nimara, A., 557
Ninomiya, K., 561
Niselson, L. A., 537
Nishida, H., 174
Nishida, T., 174
Nishimura, N., 19
Nishiyama, G., 79
Nishiyama, K., 243, 649
Nitsche, R., 547
Niwa, K., 155, 318, 575,
628
Nixon E. R., 260, 469
Nixon, J. F., 481, 501
Nizamutdinov, N. M.,
352
Nobile, A. A., 61
Noda, S., 571
Noden, J. D., 8
Nollenkle, H., 350
Noersjamsi, S., 63
Noth, H., 112, 140, 143,
144, 374,497
Nogerbekov, B. Yu., 431
Nogoev, K., 18, 95, 289
Nogues, M., 353
Nojima, M., 551
Nolin, C., 595
Noltes, J. G., 399, 413
Norbert, A., 49, 515,
638
Norbury, A. H., 635

Nord, A. G., 610
Norman, A. D., 105,
106, 386
Norris, C. L., 265
Nonvood, l.,. S., 611
Noskov, V. G., 358
Nothe, D., 678
Novak, A., 674
Novak, D. P., 180
Novalkovskii, N. P., 623
Novick, S. E., 455
Novikova, Z. M., 68
Novitskay, G. N., 390
Novoselav, N. P., 24
Novozhilov, A. L., 67
Novoselova, A. V., 75,
76,78,100
Nowacki, W., 543
Nowak, A. V., 150
Nowotny, H., 171, 173,
174,235,237,425
Nozaki, T., 236
Nriagu, J. O., 413, 521
536
Nuallain, C. 6 ,
Nunn, E. K., 364,457
Nurminskii, N. N., 61
Nurotdinov, I. A., 482
Nussbaum, A., 635
Nyberg, B., 52, 221, 614
Oakley, R. T., 51 1
Oates, G., 358, 661
Oberhammer, H., 518
Oberiin, M., 238
Obi, K., 294
Obolonchik, V. A., 649
Oboznaya, L. I., 52, 584
Oboznenko, Yu. V., 184
Obukhova, 0. P., 416
Oddon, Y., 221
Oden, L. L., 207
Odent, G., 351
Odintsev, V. V., 173
Odom, J. D., 105, 106,
142, 145, 150,469,470
Oe, S., 526
ohrn, Y., 271, 454,466
Oei, D. G., 9, 10, 576
Oertel, R. P., 92
Oye, H. A., 43, 65, 66,
69, 195, 197
Ogawa, M., 561
Ogden, J. S.,352,561
Ogenko, V. M., 318
Ogimachi, N. N., 659
Ogilvie, J. F., 257, 445
Oguni, N., 186
OHare, P. A. G.,35
Ohashi, S., 516, 525
Ohkita, K., 231
Ohno, K., 296
71 1
Author Index
Ohtaki, H., 13
Oka, S., 18
Okabe, H., 259
Okafo, E. N., 254
Okawara, R., 364
Okazaki, N., 629
OKeefe, J. G., 155
Okhlobystin, 0. Yu.,, 304
Okuda, T., 197,215
Okumura, A., 629
Okunaka, M., 312
Olah, G. A., 111, 654,
663, 670, 676
Olander, D. R., 233
Oldershaw, G. A., 272,
575
Olie, K., 484,493
Olin, A., 354
Oliver, B. G., 278
Oliver, J. P., 388
Olofsson, G., 550
Olofsson, O., 468
Olsen, D. K., 4
Olsen, F. P., 195, 597,
601
Olsen, K. J., 667
Olshevskii, M. V., 557
Olszyna, K., 435
Omelanczuk, J., 477
Onak, T., 120, 121
Onishi, T., 240
Onisor, M., 61
Onyszchuk, M., 314
Opalovskii, A. A., 240,
591
Orchard, A. F., 307
OReilly, D. E., 438
Orel, B., 194, 674
Orloff, M. K., 460
Orlova, G. M., 628
Orlova, V. T., 630
Orlovskii, V. P., 521
Orzeszko, S., 229
Osafume, K., 443
Osaki, K., 168, 264
Osborne, D. T., 267
Osborne, D. W., 50
Oselka, M. C., 650
Osipov, 0. A., 310, 394
Osokin, D. Ya., 482
Ostertag, H., 36, 67
Osterheld, R. K., 521,
522
Ostertag, H., 67
Ostrovskaya, 1. A., 274
Ott, J. B., 11, 253
Ott, R., 531, 635
Ouchi, A., 153
Ovchinnikova, V. D., I87
Ovechkin, E. K., 52, 584
Overend, J., 246, 272,
281,287
46
Overend, R., 244

Owen, T., 243
Owens, F. J., 450
Oza, C. K., 526
Ozaki, A., 423
Ozari, Y., 499, 655
Ozier, I., 296
Ozin, G. A., 315, 432,
433
Ozols, J., 53
Pace, R. J., 569
Paddock, N. L., 474
Paderno, Yu. B., 173
Padezhnova, E. M., 78
Padma, D. K., 176, 530,
591
Padrick, T. D., 465
Paetzold, R., 622,623,
635
Pagsberg, P. B., 516
Paige, H. L., 582
Paillard, C., 466
Paine, R. T., 147, 471
Painter, T. M., 501
Pakhomov, V. I., 18,
44,210, 667
Pakhomova, T. V., 427
Pal, B. B., 539
Palazzi, M., 531, 545,
585
Palen, K. M., 149
Palenik, G. J., 120, 203
Palenzona, A., 198
Palfalvi-Rozsahegyi, M., 15
Palkina, K. K., 157
Palma, T., 208, 631
Palmer, D. E., 379
Palmieri, P., 245, 255
Palvadeau, P., 179
Pan, Y.-C. E., 656
Panasenko, N. M., 191
Panchenkov, I. G., 97
Panchuk, I. E., 649
Panchuk, 0. E., 649
Pandhey, A. N., 205
Panek, P., 5 8 , 353,409
Paniccia, F., 61, 62
Panin, 0. B., 34
Pankau, H., 219
Pankratov, A. V., 183
Pankratova, V. V., 185,
357
Pannetier, G., 279, 444,
527
Pantzer, R., 479, 493
Papatheodorou, G. N.,
70, 195
Papesch, G., 171, 237
Papulov, Yu. G., 253
Paques-Ledent, M. Th.,
326
Paramzin, A. S., 42
Parasinchuk, N. S., 619
Paris, J., 187
Parish, R. V., 399
Parkash, R., 285
Parkash, S., 289
Parker, H. S., 212
Parker, V. B., 75
Parker, W., 412
Parker, W. E., 232
Parker, W. G., 188,409
Parkes, D. A., 267, 274
Parkes, J., 625
Parks, G. A., 184
Parr, R. G.,563
Parrett, F. W.,485
Parrish, D. D., 652
Parry, D. E., 39
Parry, G. S., 34
Parry, R. W., 145, 480,
48 1
Parshina, M. I., 416
Partala, A. I., 281, 613
Parthe, E., 370, 532
Parunin, 0. B., 46
Pascal, J.-L., 665
Pasdeloup, M., 162
Pashchenko, 1. S., 350
Pashinkin, A. S., 582, 632
Passmore, J., 483, 582, 62
Pastukhova, Z. V., 298
Patel, R.C., 524
Patmore, D. J., 537
Patron, L., 398
Pattison, E. B., 80
Pattoret, A., 198
Paul, I., 392
Paul, R. C., 285, 357,
365, 518,617, 621, 622
Paulat, V., 642
Paulyuchenko, M. M.,
279
Pauwels, L. J., 533
Pavlikov, V. M., 43, 156
Pavlov, V. V., 318, 321
Pavlova, L.A., 535
Pavlova, S. A,, 192, 202,
210
Pavlyuchenko, E. N., 19
Pavlyuchenko, M. M.,
221, 527
Pawley, G. S., 572
Paxson, T. E., 139
Pazdernik, L. J., 371
Pchelintseva, G. G., 355
Peace, B. W., 358
Peach, M. E., 372, 618
Peacock, G. J., 142
Pearson, T. G., 576
Pearson, W. B., 260
Pechkovskii, V. V., 76,
520, 522,620,621,632
712
Pechurina, S. Ya., 133,386
Pedak, E., 89, 578
Pedley, J. B., 147, 424
Peel, T. E., 537, 617, 672
Peirce, R. C., 105
Peisakhova, M. E., 640
PelikBnovA, M., 516
Pelliccioni, M., 521
Pelowa, P., 573
Penkett, S. A., 464, 564
Penning, D. F., 650
Pepin, C., 159, 266
Perakis, J., 198
Perales, A., 498
Percheron, A., 425,427
Peregudov, A. S., 306
Perelman, F. M., 281
Perelygin, I. S., 23
Peresvetova, L. N., 76
Peretti, E. A., 532
Perez, G., 155
Peric, Z., 8, 560
Perivet, G., 184
Perkins, P. G., 114, 161,
265,271,277, 318,516
Perminov, V. P., 78
Perner, D., 450
Perov, V. A., 544
Perrault, G., 329
Perret, R., 239
Perrot, R., 280,455
Perry, C. H. 224,440
Perry, S. L., 109
Perry, W. B., 242
Pershaw, P. S., 248
Persson, W., 10, 92
Pescia, J., 562
Peshev, P., 171
Peskin, V. F., 554
Peslyak, G. V., 221, 527
Peteri, R., 9
Petersen, O., 500
Peterson, E. M., 438
Peterson, M. B., 504
Peterson, O., 601, 604
Peterson, S. W., 682
Peterson, W. R., 383
Petrella, G., 16
Petrescu, V., 408
Petro, V. P., 483
Petrocelli, J. V., 9
Petrosyan, V. S., 314
Petrov, B. I., 133, 402
Petrov, E. S., 69
Petrov, G. I., 350
Petrov, K. I., 546, 548, 549
Petrov, S. V., 71
Petrova, G. A., 667
Petrova, L. M., 204, 301
Petrova, T. L., 326, 350
Petrovic, A., 76
Petrovskii, G. T., 65
Author Index
Petrunin, A. B., 121
Petrushevskii, M. S., 427
Petty, F., 193
Petukhov, G. G., 357
Petushkova, S. M., 528
Petz, W., 181
Petzel, T., 89, 578
Peuker, C. 306
Pevergne, G., 56, 608
Pevzner, I. Z., 334
Peyerimhoff, S. D., 434,
439
Peytavin, S., 612, 613,
629
Pfeifer, J. F., 426
Pflugmacher, C., 367, 667
Pfrepper, G., 206
Pfundt, H., 69
Philippot, E., 51, 370,
475, 519, 586, 629
Phillips, D. T., 519
Phillips, E. C., 45
Phillips, E. W., 679
Piacente, V., 10, 11, 427
Pichugina, E. K., 315
Pickett, H. M., 254
Pidcock, A., 315, 365
Piercy, R., 151
Piermarini, G. J., 249
Pierrard, C., 384
Pierrotti, R. A., 171
Pieschel, F., 441
Piffard, Y.,220
Pijpers, F. W., 25
Pilbrow, J. R., 185
Pilcher, G., 244
Pilipchenko, V. N., 19, 612
Pilipovich, D., 259, 594,
658, 659, 664
Pillinger, C. T., 225
Pimentel, G. C., 252,
436, 465, 651, 671
Pinaev, G. F., 76, 620,
62 1,632
Pincelli, V., 148
Pinchas, S.,519
Pinchuk, A. M., 377
Pinchuk, V. V., 197
Pines, A., 441
Pinnavaia, T. J., 332, 333
Pinnington, E. H., 1
Pinsker, Z. G., 223
Pinsky, M. L., 113
Pinson, J. W., 293
Pistorius, C. W. F. T.,
224,286
Pittam, D. A., 244
Pizzino, T., 367
Plambeck, J. A., 217
Planckaert, A. A., 147
Platonov, A. N., 575
Plekhov, V. P., 309
PleHek, J., 108, 109, 125,

127, 128, 132, 133, 139
Pletcher, D., 651
Pletenets, S. S., 6
Pletka, H. D., 301
Pletnev, A. I., 310
Ploog, K., 103, 160
Plotnikov, Yu. V., 96
Plowman. K. R., 437
Pluth, J. J., 329
Plyshevskii, S. V., 520
Plyushchev, V. E., 16,
19, 44,281, 548, 549,
613, 662
Pobedimskaya, E. A.,
583
Pochkaeva, T. I., 100
Podlesskaya, A. V., 44
Podmogilnyi, E. V., 619
Ponicke, K., 361
Pogarev, D. E., 220
Pogodina, L. A., 185,
357
Pohl, S., 51, 369, 585,
599
Poindexter, E. H., 504
Poix, P., 353
Pokhudenko, V. N., 279
Pokorny, J., 33
PokriC, B., 422, 557
Pokrovskaya, L. I., 16,
662
Poland, J. S., 178, 214,
424
Poletaev, I. F., 18
Polishchuk, S. A., 204
Pollard, D. R., 505
Pollock, E. N., 619
Pollock, T. L., 295, 651
Polotebnova, N. A., 518,
519
Polshin, E. V., 339
Poltavtsev, Yu. G., 228,
581, 626,628, 649
Poltavtseva, I. G., 18
Poluektov, N. S., 100
Polukarov, A. N., 53, 581
Polyakova, V. B., 111
Polynova, T. N., 84
Pomerantseva, A. V., 60
Pomkarov, A. N., 584
Pommier, J., 360
Pomposiello, C., 249
Ponomarenko, V. A., 408
Ponomarov, V. I., 632
Pontchour, C., 468
Pontonnier, L., 74
Poocharoen, B., 360
Pope, B. M., 364
Pope, C.G., 344
Pope, M. T., 519,657
Popitsch, A., 609
71 3
Author Index
Popolitov, V. I., 554, 644
Popov, A. I., 497
Popova, S. V., 559, 628
Popovich, M. P., 272
Popovkin, B. A., 53
Porai-Koshits, M. A., 84,
515, 656
Poroshina, I. A., 202, 328,
339
Porritt, C. J., 314
Porter, R. F., 105, 140
Porter, S. K., 552
Portier, J., 218, 222
Post, B., 58
Postma, H. J., 602
Potard, C., 635
Potemin, S. S., 34
Potemin, Yu A., 68
Potenza, J., 414
Potenza, J. A., 504
Potier, A., 201, 206, 669
Potier, J., 665
Pott, G. T., 189, 341
Pottie, R. F., 532
Pottier, M. J., 327, 352
Potts, A. W., 307
Potvin, H., 449
Poupko, R., 15
Pouradier, J., 616
Pourcelly, G., 438
Powell, F. W., 267, 272
Powell, F. X., 260
Powell, G. L., 1
Powell, P., 161
Powell, R. E., 616
Poyntz, R. B., 605
Pozdeev, V. V., 299
Pozhidaev, A. I., 84
Pozonyakov, D. V., 270,
274
Pozonyakova, V. M.,
228, 581, 626, 628
Pradhan, M. M., 634
Prakash, H., 506
Prakash, S., 325
Prasad, H. S., 546, 555
Prasad, R. N., 182, 367
Prelesnik, B., 632
Prentice, J. B., 477
Pressl, K., 495
Preston, K. F., 591
Preti, G., 395
Pretzer, W. R., 107, 128
Preudhomme, J., 202
Preut, H., 386
Prevot, F., 483
Pribylov, K. P., 621
Price, D. L., 50,286
Price, G. H., 613
Price, S. J., 217
Prigozhina, L. D., 298
Prikhod'ko, R. I., 635
Prince, R. H., 569

Pringle, W. C., jun., 105
Priore, D., 61
Prisyazhnyi, V. D., 65
Pritchina, T. G., 468
Prods, A. M., 327, 352
Prodan, E. A., 221, 279,
527
Prodan, L. I., 221, 527
Prokhorova, N. P., 102
Prokhvatilov, A. I., 249
Prokof'ev, A. K., 304
Prokopchuk, Yu. Z., 102
Prons, V. N., 508
Prosen, E. J., 669
Proskurin, V. N., 10
Proskurnina M. V., 515
Prost, M., 55, 265, 578
Protas, J., 425, 570
Prothero, A., 409
Protsenko, P. I., 61, 220,
454, 461
Prout, C. K., 502
Prout, E. G., 449
Prout, K., 178
Pruntsev, A. E., 18, 195
Prutton, M., 80
Pryakhina, N. P., 344
Prymova, L. A., 630
Ptushkina, M. N., 518
PuEar, Z., 422, 557
Pucciarelli, F., 574
Pucheault, J., 617
Pudovik, A. N., 309
Pugh, L. A., 243
Pullin, A. D. E., 287,
436
Pupp, C., 532
Pupp, M., 644
Purcell, K. F., 434
Puri, B. R., 231
Puri, J. K., 365, 589, 617
Purnell, J. H., 403
Purwins, H.-G., 198
Pushkareva, K. S., 310
Pushkina, G. Ya., 542
Pushnyakova, V. A., 279
Pustelnik, N., 30
Putaux, J. C., 45
Puxley, D. C., 410
Puzic, 0. S., 579
Puzyrevskaya, 0. M., 315
Quail, J. W., 659
Quareni, S., 337
Quarterman, L. A., 44,
557, 659
Quieley, T. A., 237
Quimby, 0. T., 477
Rabalais, J. W., 436
Rabe, W., 65
Rabenau, A., 554,584,639

Rabenstein, D. L., 422
Rabinovich, I. B., 402
Rabinovich, V. A., 224
Rabinovitch, B. S., 257
Rachinskii, V. V., 89
Rackwitz, D., 469
Radautsan, S. I., 211, 588
Radchenko, I. V., 64
Radell, J., 383
Rademacher, P., 443
Radheshwar, P. V., 540,
558
Radicheva, G. V., 527
Radler, K., 4
Radonovich, L. J., 383
Radosavljevic, S. D., 301
Rauber, A., 193
Rafaeloff, R., 661
Rafalski, W., 82
Rai, D. N., 128, 134
Raichenko, T. F., 193
Raith, W., 565
Rajaram, J., 217
Rajeswari, S., 603
Rajnvajn, J., 674
Rake, A. T., 392
Rakhimbekova, Kh. M.,
527
Rakita, P. E., 398
Rakke, T., 545
Rakotomohanina, E., 527
Ram, U. S., 235
Ramachandran, V. S., 335
Ramakrishna, J., 263
Ramakrishna, R. S., 21 1
Ramakrishna, V., 537
Ramanujam, P. S., 264
Rambidi, N. G., 45, 155,
612
Ramirez, F., 516
Ramos, V. B., 360
Ramsay, D. A., 260
Ramsey, R. N., 171
Ranade, S. N., 636
Randaccio, L., 32, 3 11,
369,440
Randall, R. S., 313
Ranganathan, T. N., 509
Rankin, D. W. H., 292,
398, 449, 473, 489,
490,494, 501
Rao, G. B. B., 442
Rao, G. G., 442
Rao, G. S., 552
Rao, K. N., 243
Rao, K. S. M., 491
Rao, K. V. S., 499, 596
Rao, M. S., 277
Rao, P. V. K., 442
Rao, S. V. C., 365
Raper, 0. F., 463
714
Rapp, B., 145, 470
Rasmussen, S. E., 33, 154
Raspopin, S. P., 68, 71,
408
Ratcliff, B., 392

Rath, J., 218
Rathke, J. W., 109, 110,
159
Rathousky, J., 298

Ratkje, S. K., 473
Ratov, A. N., 346
Rau, H., 554, 584, 639
Rauber, W. ,422
Raveau, B., 219, 554,558
Rawat, P. C., 422
Ray, B. J., 568
Ray, M. N., 263, 412
Ray, N. N., 74, 75
Raymond, K. N., 31
Raymonda, J. W., 246
Razuvaev, G. A., 389,
401
Rea, J. R., 522
Reader, J., 10, 39
Rebsch, M., 606
Rechenberg, W., 657
Recker, K., 71
Reddy, P. R., 526
Redwood, M. E., 389
Ree, K. H., 482
Reeder, J., 253
Reeves, L. W., 220, 306,
562
Regen, S. L., 163
Reger, A., 81
Reichenbach, G., 655
Reichenbacher, M., 622
Reichert, B. E., 389
Reichert, W. L., 623
Reichman, S., 483
Reikhsfeld, V. O., 361
Reilly, J. P., 162
Reilly, T. J., 122
Reiner, D., 497
Rembaum, A., 21
Remizovich, T. V., 628
Renaud, R., 552
Rendle D. F., 200
Renier, D., 144
Renniger, A. L., 545,
619, 627
Renucci, J. B., 620
Renz, W., 466,656
Reshetova, L. N., 76
Retcofsky, H. L., 230
Rettig, S. J., 507
Retvert, R. J., 530
Reutov, 0.A., 314
Reversat, G., 45
Revzin, G. E., 204, 208,
301
Revzlna, T.V., 194, 63 1
Author Index
Rey, C., 523, 562
Reznik, A. M., 16
Reznik, B. E., 518
Rezvukhin, A. I., 219
Rhine, W., 31
Ribar, B., 76
Ribnikav., S. B., 579
Rice, S. A., 568
Richard, P., 4, 519
Richard, J. P., 217
Richards, R. E., 658
Richards, S. R.,407
Richardson, D. M., 67
Richez, J., 9
Richmond, J. R., 301,
302,450
Richter, M. J., 450
Richter, P. W., 224, 286
Richter, W., 620
Riddel, J. D., 459
Riddle, C., 160, 294
Ridge, M. J., 280
Ridley, B. A., 266, 273,
562
Ridley, D. C., 506
Riegel, D., 649
Riegel, F., 169, 633
Riera, V., 395
Riess, J. G., 486, 495
Riethmiller, S., 145, 470
Rietz, R. R., 106, 109, 116
Rigaut, M., 233
Righetti, E., 23
Riley, P. E., 342
Riley, S. J., 303
Rimler, B., 224
Rimlinger, L.,426
Rimsky, A., 199
Rinaldi, R. P., 572
Ring, M. A., 293, 294,
403,479
Rinnan, B., 68
Ripmeester, J. A., 440
Rippon, D. M., 247,466
Rittig, F. R., 168
Riveros, J. M., 656, 676
Rivet, J., 369, 370, 585,
626, 647
Rivkin, M. N., I89
Riviere-Baudet, M., 381
Robb, M. A., 256
Robbins, M., 193
Robert, D. U., 486
Robert, J.-B., 469
Robert, M. C., 238
Roberts, D. H., 179
Roberts, J. H., 437
Roberts, J. R.,384
Roberts, M. W., 270
Roberts, P. J., 650
Roberts, R. M. G., 392
Robertson, A., 449
Robertson, J. M., 502

Robin, H. B., 246
Robin-Chassain, Y.,
36
Robineau, M., 93, 277
Robinson, A., 392
Robinson, D. J., 189
Robinson, M. G., 251
Robinson, P. D., 191
Robinson, P. L., 576
Robinson, W. R., 215
Robinson, W. T., 390,544
Robkov, E. U., 591
Robov, A. M., 224
Roca, M., 104
Roch, R. R., 199
Roche, A. L.,514
Rochev, V. Ya., 314
Rock, P. A., 14
Rock, S. L., 265,284
Rode, B. M., 146,263,
287,472,673
Rodesiler, P. F., 375
Rodger, M., 372
Rodicheva, G. V., 209
Rodina, T. F., 216
Rodionov, E. S., 497
Rodionova, N. A., 18,
19,461
Rodziewicz, W., 370
Rodzolko, Yu. G., 303
Roe, A. N., 444
Roelle, W., 378
Rosch, L., 382
Roesky, H. W., 379, 493,
500,501, 503, 506,
529, 599, 601, 604
Roetnes, M., 68
Rogers, M. T., 537
Rogl, P., 171, 173
Rogstad, A., 542, 573
Rohmer, R., 75
Rohrbaugh, W. J., 529
Rohwer, H. E., 499
Roi, N. I., 553
Kokhljna, E. M., 306
Roland, G., 309, 518, 537
Rolfe, J., 566
Rolin, M., 438, 671
Romano, V., 367
Romanov, 0.A., 613
Romanov, V. F., 522
Romashov, V. D., 545
Romm, I. P.,197,206
Ronomi, G. N., 78
Ronova, I. A., 304
ROOS,G., 216, 643
Roques, B., 425
Rose, 3. E.,317
Rose, J., 431
Rose, P. D., 293
Roseberry, T., 106
Rosen, E., 9
Author Index
Rosenber, I., 171
Rosenberg, A., 296
Rosenwaks, S., 266
Roshchina, A. V., 625
Rosolovskaya, E. N., 346
Rosolovskii, V. Ya., 37,
43, 57, 150, 154, 189,
196,443, 549, 567, 665,
666,668
Ross, B., 500
ROSS,J., 250
Ross, S. D., 407
Rossi, G., 329
Rossier, D., 649
Roth, R. S., 212
Rothe, E. W., 455
Rothenberg, S., 147,464,
567
Rouby, B., 158
Roudault, R., 519
Rouex, J., 222
Rouillon, J. C., 232
Rouland, J.-C., 429
Rousset, A., 187
Rouxel, J., 20, 21, 179
Rowbotham, P. J., 399
Rowe, D. M. J., 9
Rowe, J. M., 50,286
Rowlands, F. S., 251,
296, 651
Royer, J. L., 619
Royon, J., 651
Rozanov, I. A., 192, 507
Rozen, Yu.B., 334
Rozett, R. W., 107
Ruban, L. M., 12
Ruben, D. J., 247,257
Rubin, K., 254
Rubini, P., 185
Rubstov, V. P., 581
Ruchkin, E. D., 289
Ruchnova, S. A., 18, 19
Ruckman, J. C., 409
Rudenko, A. P., 346
Rudenko, N. P., 101
Rudman, R., 254
Rudolph, R. W., 107, 128,
134,471
Rudorff, W., 21,222,241
Ruff, J. K., 503
Ruland, W., 239
Rulis, A. M., 250
Rumfeldt, R. C., 217
Rumpel, W. F., 650
Rundle, H. W., 434
Rundqvist, S., 468
Runov, N. N., 19,92,95
Rupert, I., 377
Rupert, J. P., 332
Rusch, P. F., 20,437
Rush, J. J., 50
Rushnova, S. A., 461
715
Russ, C. R., 481
Russegger, P., 260
Russell, B. R., 246, 307
Russell, P. K., 151
Russell, J. D., 338
Russmore, J., 162
Rustamov, P. G., 625
Rutenberg, A. C., 149
Rutherford, J. S., 504
Ryabchenko, 0.I., 24
Ryabov, E. N., 70,71
Ryabov, Yu. S., 624
Ryan, M. P. 454
Ryan, R. R., 548
Rybakov, B. B., 515
Rycroft, D. S., 620
Rykhal, R. M., 198
Rykl, D., 340
Ryschkewitsch, G. E., 142
Rysev, A. P., 19
Ryspaev, O., 18
Rytter, B. E. D., 43, 197
Rytter, E., 43, 69, 195,
197
Ryu, J., 274

Ryutina, N. M., 68
Rza-Zade, P. F., 18, 79
Sabherwal, I. H., 473
Sabin, J. R., 145,271
Sabo, E. P., 649
Saboungi, M. L., 461
Sabrowsky, H., 222
Sacage, W.J., 292
Sacco, A., 16
Sacharov, S . G., 314
Sadanaga, R., 337
Sadikova, A. T., 661
Sadna, N. I., 254
Sadokhina, L. A., 546
Sadovskii, A. P., 271,
579, 606
Sadykov, R. H., 408

Saegusa, T., 274
Saeki, M., 244
Saeki, Y., 557
Safarik, I., 294
Safford, G. I., 15
Safin, I. Ya., 482
Safiullin, N. Sh., 191
Safonov, V. V., 253, 303,
641, 642
Sagatov, M., 580

Sahl, K., 338
Saibova, M. T., 189
St. Pierre, G. R., 427
Saito, H., 508
Saito, S., 462
Saito, Y., 541
Sakaino, K., 615
Sakakibara, A., 561
Sakamaki, T., 29
Sakk, Zh. G., 443

Sakka, S., 224
Sakovich, L. G., 300
Sakura, S., 23
Sakurai, EL, 385
Sakuri, T., 640
Saleh, G., 512
Saleh, J. M., 451
Salentine, C. G., 125
Sales, K. D., 375
Salesi, R. J., 481
Salov, A. V., 49, 554,
585,628
Salzberg, J. B., 187

Samedov, Kh. R., 87
Samoilov, 0. Ya., 16
Samoilova, S. O., 528
Samosyuk, V. N., 3
Samouel, M., 71
Samplavskaya, K. K., 57,
636
Sams, J. R., 313, 365,

366,532
Samson, J. A. R., 430,454

Samsonov, A. P., 211
Samsonov, G. V., 171,648
Samsonova, T. I., 202,339
Samuelson, E. J., 560
Samuskovich, V. V., 279
Sanchez, J. P., 315
Sanchez, M., 498
Sandercock, A., 205
Sandhu, H. S., 294,295
Sandhu, S. S., 536
Sandler, R. A., 70, 71
Sandmann, H., 475,529
Sandorfy, C., 147, 246,
284
Sanger, A. R., 485,489,

493
Sankaranarayanan, V. N.,
629
Sankhla, P. S.,261
Sans, J. R., 614
Santini, S., 655
Santoliquido, R., 199
Santry, D. P., 569
Sanyal, N. K., 205
Sanz, F., 477,487, 535
Sapova, R. G., 431
Sapozhnikov, Yu. L., 155
Sara, A. N., 303
Sarin, R., 210
Sarin, V. A., 37
Sartaniya, V. G., 508
Sartori, F., 157, 337
Sartori, P., 485
Sarudi, I., 60
Sasa, T., 197
Sasaki, Y., 468
Sata, T., 75
Satchell, R. S., 424
716
Satge, J., 381, 418, 480
Sata, M., 174
Sato, S., 155
Saturnino, D. J., 126
Satyavati, A. V., 14
Satybaldiev, O., 36
Sauer, D. T., 618
Saunders, A., 651
Saunders, V. R., 466
Sauvage, J. P., 27
Sauvageau, P., 147, 246
Savall, A., 452
Savchenkova, A. P., 77
Saveleva, L. V., 19
Saveliev, B. A., 103, 150,
482
Savenkova, M. A., 454

Savoie, R., 595
Savolainen, J. E., 67
Savory, C. G., 114
Sawodny, W., 594
Sawyer, D. T., 607
Saxena, K. L., 312, 313
Saxena, R. S.,210
Sayamyan, E. A., 18
Scantlin, W. M., 105
Scepanovic, V. C., 301
Schaad, L. J., 469
Schack, C. J., 259, 594,
659, 664
Schadow, H., 508

Schaefer, H., 11, 95, 96,
97, 195, 198,214, 308,
644,648
Schaeffer H. F., tert.,

147,257,464, 567, 676
Schaefer, T., 436

Schaeffer, R., 105, 106,
107, 108, 109, 110, 115,
116, 159
Schafer, T. P., 676
Schaper, P. W., 463
Schaper, W., 503
Schardt, K., 366
Schartau, W., 46, 325,
327, 351
Schartz, M., 248
Schatz, J. , 483
Schaub, B., 635
Schehl, R. R., 230
Scheidt, W. R., 383
Scheie, C. E., 438
Scheler, H., 508
Schellhaas, F., 367, 667
Scheludyakov, V. S.,
497
Scherbakov, V. N., 338

Scherer, J. R., 570
Scherer, 0. J., 495
Scheringer, C., 521
Scherr, V. M., 161
Scherubel, G. A., 359
Author Index
Schichl, H., 56, 333
Schiller, W., 408
Schillings, K. L., 5
Schindler, N., 492, 502
Schindler, R. A., 463
Schippers, A. B. A., 42
Schiwy, W., 51, 369, 370,
585
Schlak, O., 504

Schlegel, J. M., 61
Schlein, W., 21 1
Schlemper, E. O., 360
Schlosberg, R. H., 670
Schlueter, M., 624
Schmelzer, W. , 168, 605
Schmelzer, W., 605
Schmid, G., 181, 304,
393,404, 521
Schmid, K. H., 80, 164,

383
Schmid, P., 382, 480, 534

Schmidbaur, H., 357,
479,489
Schmidpeter, A., 502,

508, 513
Schmidt, A., 495, 550,

551, 552
Schmidt, F. J., 619

Schmidt, M., 168, 471,
572
Schmidt, P., 377

Schmidt, V., 222
Schmidt, W., 479, 573
Schmidt-Sudhoff, G., 112
Schmutzler, R., 486,488,
504
Schneemayer, L. F., 671
Schneer-Erdey, A. , 678
Schneider, I. A., 217,
218,244
Schneider, J., 193

Schneider, J. A., 659
Schneider, P., 291
Schneider, S., 524
Schnepp, 0., 43 1
Schniedel, H., 219
Schnitt, T., 588
Schnuelle, G. W., 563
Schon, G., 201
Schon, H., 677
Scholer, F. R., 119, 127
Scholz, K. L., 650
Schonfeld, I., 649
Schoonveld, L. H., 282
Schott, G., 291
Schram, E. P., 143, 170
Schrauzer, G. N., 432
Schreiber, H. C., 590
Schreiner, A. F., 211
Schrey, F., 96, 363
Schrieke, R. R., 389
Schriver, L., 288
Schrobilgen, G. J., 152,

679
Schroeder, D. R., 548

Schroder, H. H. J., 471
Schropfer, L., 614
Schubert, A., 461
Schubert, K., 198
Schuer, H., 554
Schug, J. C., 656
Schuhmacher, M., 547
Schumacher, H. J., 655,
665
Schumann, H., 372, 382

Schumann, H.-D., 535,
536
Schumann, K., 513

Schultz, E., 526
Schultze-Rhonhof, E., 187
Schulz, D. N., 546
Schulze, H., 628
Schussler, D. P., 215
Schuster, P., 260, 674
Schwartz, A. W., 516
Schwartz, L. D., 147, 534
Schwartz, M. E., 431
Schwarz, M., 143
Schwarz, W., 168, 605
Schwarz, W. H. E., 678
Schwarzenbach, G., 211
Schwedes, B., 558
Schweiger, J. R., 433, 494
Schweitzer, G. K., 245,
307
Schwertnerova, E., 442

Scibelli, J. V., 418
Scordari, F., 186
Scott, F. A., 5
Scrimshaw, G. F., 249
Scrosati, B., 3
Seal, R. K., jun., 454
Seale, S. K., 179
Sealy, B. J., 649
Searcy, A. W., 204
Sears, C. T., jun., 469
Sears, W. G., 449
Seccombe, R. C., 412
Seel, F., 591
Seeley, R., 613
Sefcik, M. D., 293, 403
Seff, K., 189, 341, 342
Segev, M., 505
Sehested, K., 667
Seidl, V., 553
Seidor, F. M., 625
Seifer, A. L., 16
Seifert, F., 338
Seifert, H. J., 70
Seifullina, I. I., 315
Seip, H. M., 164, 168,
605
Seip, R., 164, 168, 605

Seleznev, B. L., 19
Author Index
Selig, H., 490, 661, 679,
681
Selig, W., 657
Selivanova, G. A., 524
Selivanova, N. M., 629,
630,631
Sellers, R. M., 263
Selte, K., 468, 532, 533
Semenenko, K. N., 50,
77, 111, 112, 175, 176,
180
Semikina, L. E., 310
Semiletov, S. A., 211, 588
Semin, G. K., 308, 314,
542
Semvad, E. E., 587
Sen, B., 182
Sen, D., 165
Sen, D. N., 77
Senda, T., 525
Seng, N., 487
Sengupta, A. K., 19
Sengupta, K. K., 516,539
Senozan, N. M., 22
Seppelt, K., 622, 623,
624, 663, 678
Sequeira, M. R., 51, 461
Serebrennikov, A. I., 611
Serebrennikov, V. V.,
300, 353, 370,476, 531
Serebrennikova, G. M.,
642
Sereda, P. J., 335
Seregin, P. P., 580
Serezhkin, V. N., 75, 76
Serezhkina, L. B., 75, 76
Sergeeva, V. P., 517
Seshadri, K. S., 436
Setaka, M., 611
Sethuraman, P. R., 644,
647
Setkina, V. N., 315
Setzer, D. W., 250, 267,
281, 297
Sevastyanov, A. I., 101
Seymour, S. J., 472
Shackelford, S. A., 682
Shaffer, J. H., 67
Shafir, J. M., 217
Shagidullin, R. R., 535,
540
Shahid, K. A., 331
Shahid, M. S., 603
Shakhpironov, M. I., 213
Shalaeva, 0. N., 183
Shalimova, K. V., 584
Shamaev, P. P., 156
Shamaiko, L. P., 201
Shamba, E. M., 353
Shamir, J., 552, 661,
662, 670
Shamsuddin, M. S., 580
717
Shanbhag, S. V., 529
Shancke, P. N., 453
Shannon, D. W., 5
Shannon, R. D., 353,
410, 519, 553
Shaplygin, I. S., 354
Shapovalov, A., 58
Sharipov, D., 492
Sharma, D. K., 214
Sharma, J., 54
Sharma, L. H., 288
Sharma, P. D., 217, 552
Sharma, R. A., 3, 576
Sharma, R. D., 621, 622,
636
Sharma, R. K., 357
Sharma, S. K., 325
Sharopin, A. N., 431
Sharov, A. F., 67
Sharov, V. N., 508
Sharp, D. W. A., 591
Sharp, K. G., 255, 305
Sharp, R. R., 658
Sharpless, R. L., 464
Shashkin, D. P., 87
Shatskii, V. M., 276
Shaw, E. T., 507
Shaw, J. H., 563
Shaw, R. A., 506,507,
508, 511, 530
Shaw, R. W., jun., 482,
591, 658
Shcheglova, V. D., 44
Shchegolev, B. F., 183, 316
Shchegrov, L. N., 522, 570
Shchepochkina, N. I., 192
Shcherbak, L, P., 649
Shcherbakov, V. K., 53,
149
Shcherbina, U. V., 575
Shchupak, E. A., 388
Shea, M. J., 409
Shearer, J. A., 187, 335
Sheehan, D. F., 659
Sheka, I. A., 279, 554,585
Sheka, V. I., 582
Sheldrick, G. M., 545, 627
Sheldrick, W. S., 486, 488
Sheludyakov, V. D., 364
Shen, J., 654, 670, 676
Shen, J. H., 319
Shenhav, H., 115
Shenkin, Ya. S., 18, 19,
46 1
Shepelev, Yu. F., 46,
325, 327, 331
Sheppard, N., 248
Shereshkova, V. I., 212
Sherwood, P. M. A., 506
Shestakov, E. E., 361
Shevchenko, V. I., 513
Shevchik, N. L., 78
Shevchuk, I. A., 524

Shevchuk, V. G., 18, 19,
191, 192, 613
Shevelkov, V. F., 58,
212, 624, 625
Sheverdina, N. I., 299,
304
Shevlin, P. B., 226, 265
Shevtsov, L. V., 565
Shevtsova, I. N., 52,
Shevtsova, L. N., 584
Shiba, F., 551
Shibaeva, R. P., 361
Shibanov, E. V., 335
Shibuya, T., 431
Shields, H., 462
Shields, K. G., 412
Shigemoto, H., 215
Shigina, L. N., 350
Shih, S., 434
Shillady, D. D., 143, 439
Shilov, A. E. , 43 1
Shilova, A. K., 431
Shiina, K., 372
Shimanouchi, T., 247
Shimizu, H., 58
Shimp, L. A., 113, 226,
23 8
Shindler, Yu. M., 431
Shinik, G. M., 519
Shinmei, M., 318
Shinyaev, A. Ya., 426
Shiokawa, J., 554
Shiorini, T., 501
Shiotani, A., 357
Shipilova, E. M., 631
Shirinskaya, L. P., 344
Shirk, A. E., 111, 175
Shirley, D. A., 39
Shirokova, G. N., 57, 189
Shirvinskaya, A. K., 336
Shiryaev, V. I., 300
Shishido, T., 171
Shishkin, Yu. A., 297
Shishkina, Z. I., 409
Shitov, 0. P., 159
Shitov, V. A,, 325
Shitova, V. I., 336, 352
Shklobed, V. E., 394
Shkodin. V. G., 632
Shkolnikov, E. V., 628
Shlyapochnikov, V. A.,
256
Shmanenkova, G. I., 199
Shmelkova, G. F., 220,
461
Shmydko, L. I., 556
Shnaiderman, S. Ya., 202
Shpakova, V. M., 524
Shpikula, V. M., 19, 612
Shporer, M., 15
Shokarev, M. M., 276
718
Shokin, I. N., 19
Shokol, V. A., 503
Sholts, V. B., 40, 42, 69
Shore, S. G., 106, 107,
113, 114, 126, 163, 483
Shorokhura, V. I., 552
Showell, J. S., 519
Shreeve, J. M., 362,
465, 482, 591, 593, 618
Shriver, D. F., 111, 175,
185, 550
Shterenberg, L. E., 227
Shtern, M. A., 409
Shtin, A. P., 522
Shtokalo, M. I., 199
Shubaeva, M. A., 344
Shuko, T. A., 281
Shultin, A. A., 220
Shulyak, L. F., 18, 19,
46 1
Shumeiko, L. I., 213
Shumov, Yu. A., 65
Shurginov, E. A., 408
Shurvell, H. F., 249, 257
Shu-shou-sen, S., 198
Shuster, Ya. A., 310
Shustov, L. D., 678
Shutyi, L. L., 526
Shuvalov, L. A., 632
Shvangiradze, P., 649
Shvedov, V. P., 61, 65
Shveikin, G. P., 236
Shvets, V. I., 649
Sichel, J. M., 565
Siddiqi, K. S., 315
Sidnenko, E. V., 519
Sidorenko, F. A., 427
Sidorov, L. N., 40, 42, 69
Sidorova, E. E., 621
Siebert, H., 666
Siebert, W., 168, 169,
605, 633
Siedle, A. R., 106, 1 16
Siefert, H., 445
Siegbahn, H., i04, 271,
578
Siegbahn, K., 39, 104,
271,436, 578
Siemens, R. E., 207
Siew, P. Y., 307
Siftar, J., 194
Sigula, N. I., 204, 547,
612
Sihada, A.-F., 492
SillCn, L. G., 522
Sillion, B., 320
Silver, J., 407
Silvers, S. J., 147, 493
Sim, G. A., 180
Simic, R., 567
Simmon, J. H., 155
Simon, A., 37, 535, 536
Author Index
Simon, G. L., 392
Simon, J., 81
Simonaitis, S. R., 267, 464
Simonnin, M.-P., 494
Simonov, M. A., 87, 326,
350, 351
Simonov, V. I., 329, 629,
632
Simons, J. W., 295
Simpson, J. B., 282
Simpson, S. R., 452
Simpson, T., 390
Sinclair, T. J., 272, 579
Singh, B. R., 100
Singh, G., 14, 235
Singh, H. B., 203
Singh, H. P., 216
Singh, R. P., 203
Sinha, R. K., 232, 590
Sinitsyna, N. A., 304
Sinnarkar, N. D., 263, 412
Sirmokadam, N. N., 312,
315
Sishkina, Z. I., 157
Sisido, K., 381
Sisler, H., 506
Sitnikov, V. V., 6
Siu, A. K. Q., 74
Sizova, R. G., 327
Skaates, J. M., 299
Skabichevskii, P. A., 23
Skachkov, A. N., 183
Skamp, K. R., 142
Skaug, K. E., 533
Skell, P. S., 226
Skeoch, K. G., 555, 636
Sklyarov, A. W.,268
Skolnik, E. G., 481
Skopenko, V. V., 92
Skopopanov, A. S., 427,
429
Skorupowa, E., 516
Skranovskjr, S.,501
Skripkin, V. V., 394
Skripnichenko, R. M., 18
Skvortsov, V. G., 18, 155
Skvortsova, G. G., 315
Sladkov, A. M., 230
Sladky, F., 153, 357, 643
Sladky, F. O., 613
Slager, T. L., 270, 589
Slanger, T. G., 464
Sleight, A. W., 409, 584
Slesarev, V. N., 227
Slinkin, A. A., 298
Sliuc, E., 188
Slivko, T. A., 613
Sloane, T. M., 250
Slobodchikov, A. M., 92
Slobodyanyuk, A. A., 202
Slobol, L. G., 629
Smagulova, A. M., 351
Smail, E. J., 545

Smail, J., M., 627
Smalley, R. E., 287
Smallwood, R. J., 375
Smardzewski, R. R., 561
Smarina, E. I., 625
Smart, R. St. C., 270
Smid, J., 95
Smirnov, M. U., 65, 67
Smirnov, V. A., 183
Smirnova, G. M., 157,409
Smirnova, N. L., 608
Smith, B. C., 507, 51 1
Smith, B. E., 112
Smith, B. L., 437
Smith, C. A., 36
Smith, D. F., jun., 151,
287, 563
Smith, D. L., 8
Smith, D. P., 519
Smith, D. W., 250
Smith, F. J., 555
Smith, G. P., 555
Smith, G. R., 406
Smith, H. E., 497
Smith, 1. W.M., 266, 273
Smith, J., 436
Smith, J. A. S., 264, 667
Smith, J. D., 180
Smith, J. G., 282
Smith, J. V., 201, 329
Smith, L. E., 98
Smith, M. B., 177
Smith, M. C., 228
Smith, R. H., 263
Smith, T. D., 185, 201
Smith, T. W., 317
Smith, W. H., 265
Smolin, Yu. I., 46, 325,
327, 331
Smorodinskaya, Zh. Ya.,
232
Smrchek, V. A., 197
Smyshlyaev, S. I., 351
Sneath, R. L., 117
Sneddon, L. G., 105,
108,120,122
Snelson, A., 43, 151, 193
Snider, A. M., .iun., 482
Snider, D. E., 563
Snow, M. R., 593
Snyder, W. R., 590
So, S. P., 664
Sobol, L. G., 631
Soboleva, L. V., 44
Soboleva, P. A., 328
Soboleva, S. V., 325
Sochneva, V. A., 524
Sodd, V. J., 650
Sodeck, G., 147,471
Sonderquist, R., 354
Sofue, A., 557
Author Index
Sogabe, K., 274
Soklakov, A. I., 44
Sokol, V. I., 192, 507
Sokolchik, A. A., 192, 520
Sokoloff, J. B., 440
Sokolov, A. B., 208
Sokolova, N. P., 270, 274
Sokolskii, D. V., 431
Solomon, I. J., 454
Solomon, P., 675
Solomonik, V. G., 40
Soloniewiez, R., 30
Solotovitskaya, E. S., 61
Solovev, A. N., 5 , 19
Soloveva, V. N., 608
Soma, M., 240
Sommer, L. H., 384
Somoano, R. B., 21
Songstad, J., 635
Sonntag, B., 4
Sorarrain, 0. M., 152
Sorriso, S., 394
Sosnina, I. V., 304
Sosnovskaya, L. K., 68
Sotnikov-Yuzhik, Yu. M.,
221, 527
Sotnikova-Yuzhik, V. A.,
221, 527
Souleau, C., 370,426,429
Southern, J. T., 548, 554
Sowerby, D. B., 505,
510, 511
Spalding, T. R., 307
Spannhake, N., 531, 618,
635
Speirs, G. K., 254
Speiser, S., 252
Spencer, J. B., 617
Spencer, J. C., 131
Spencer, J. N., 45, 590
Sperling, H. P., 261
Spialter, L., 296
Spicer, C. W., 464
Spickett, J. T., 314
Spielvogel, B. F., 167
Spierenburg, J., 363
Spiker, R. C., 35, 451,
563, 564
Spinney, H. G., 306, 392
Spiridonov, V. P., 213
Spiro, T. G., 482
Spitsbergen, U., 409
Spitsyn, V. I., 678
Spofford, W. A., 307
Sprecher, R. F., 109
Srivastava, B. B., 205
Srivastava, G., 169, 357,
360, 361
Srivastava, H. N., 529
Srivastava, T. N., 312,
313, 383
Stacey, M., 143
71 9
Stahlin, W., 207
Staendeke, H., 466
Stafford, F. E., 147, 471
Stalhandske, C., 44
Stalick, J. K., 406
Stamboni, V., 426
Stamnes, H., 65
Stamper, P. J., 392
Stanko, V. I., 131, 132,
133, 388
Stanley, E., 94
Stapfer, C. H., 363
Starks, R. G., 412
Starodubceva, R.V., 346
Stary, H., 508
Stasi, M., 174
Staubwasser, W., 5
Stauffer, D., 435
Stearns, C. A. , 177, 179,
235
Stec, W. J., 39, 528, 531,
546
Stedman, D. H., 281
Steeb, S., 78
Steel, F., 588
Steel, W. C., 81
Steiger, R. P., 193
Stein, F. P., 418
Stein, G. D., 273
Stein, L., 676
Steinberg, K.-H., 324
Steinberger, H., 479
Steiner, W. A., 268
Steinfeld, J. I., 150
Steinfink, H., 96, 370,
587, 626, 638
Steinwandter, H., 640
Stelzer, O., 372
Stengle, T. R., 656
Stepanishchev, S. V., 354
Stepanov, B. I., 197
Stepanov, V. P., 67
Stepanyan, A. E., 253
Stepin, B. D., 303, 595,
642
Stepina, E. M., 300
Stepina, S. B., 19, 44, 662
Stepovik, L. P., 185, 357
Sterberg, S.,408
Sterenberg, I. E., 230
Sterlin, S. R., 402
Sternberg, S., 66
Sterzel, W., 278, 618, 669
Steudel, R., 602, 606
Stevens, G. C., 244
Stevens, J. R., 431
Stevenson, P. E., 113
StevoviC, J., 184
Steward, D. J., 409, 553
Stewart, D. T., 195
Stewart, G. W., 295
Stewart, J. J. P., 114
Stewart, M., 230

Stibr, B., 108, 109, 125,
128
Stiubiano, G., 393
Stkacheva, Z., 340
Stobart, S. R., 290, 371,
389, 392, 393,413
Stobbs, L., 501
Stockbauer, R., 243
Stoitschewa, M.,629
Stojakovic, D. R., 301
Stokes, F. C., 308, 547,
640
Stoklosa, H. J., 528
Stolyarov, V. L., 200
Stone, F. G. A., 131, 395
Stone, F. J., 346
Stopschinski , W. , 33
Storch, W., 144,497
Storms, E. K., 237
Storozhenko, V. N., 67
Storr, A., 200
Story, H. S., 209
Stout, N. D., 103, 173
Strandberg, R., 518
Stranks, D. R., 205
Straty, G. C., 650
Straughan, B. P., 485
Strauss, A. J., 454, 626
Strauss, H. L., 248
Strauss, I., 77
Strausz, 0. P., 294, 295
Strazhesko, D. N., 231
Streba, E., 393
Strecker, S., 657
Strelets, Kh. L., 67
Strey, G., 472
Strich, A., 482
Strizhov, N. K., 209
Strocka, B., 409
Stroebel, H. A., 569
Stroganov, S. S., 431
Strongin, B. G., 619
Strouf, O., 177
Strouse, C. E., 138
Stroyer-Hansen, T., 573
Stroz, D. A., 422
Struchkov, Yu. T., 304,
357, 394
Stuart, W. I., 613
Stuchlik, J., 132
Stucky, G. D., 31, 129
Stuhler, H., 479, 489
Stuehr, J. E., 84
Stufkens, D. J., 493
Stuhl, F., 267, 463
Stukalo, E. A., 484
Stukovenkov, L. M., 67
Sturre, I. G., 101
Su, Y. Y., 402
Subramanian, S., 536
Subtil, J. L., 1
720
Suchan, H. L., 39
Suchilnikov, S. I., 427
Suchow, L., 202
Sudarsanen, K., 523
Suffolk, R. J., 261
Suggitt, C., 265
Sukhenko, V. D., 554,585
Sukhomlinov, A. B., 310
Sukhoverkov, V. F., 661
Sulaimankulov, K., 18,
95,289
Suleimanova, M. G., 377
Suleman, M., 80
Suliman, M. R., 143, 170
Sultanov, A. S., 213
Sultanova, R. Kh., 533
Sumarokova, T. N., 408
Sumitani, K., 292
Sun, T. S., 272
Sunin, A. N., 69, 194
Suri, S. K., 537
Surles, T., 44, 557, 659
Surpina, D. E., 408
Sushkova, S. G., 157, 409
Suslova, G. D., 409
Susmann, S., 50, 286
Susskind, J., 243
Sutcliffe, G. D., 178
Suter, R. W., 483
Sutherland, H. H., 212,
625
Sutherley, T. A., 452
Suvorov, A. V., 492
Suvorova, N. V., 351,355
Suznjevic, C., 236, 468
Suzuki, I., 247
Suzuki, S., 199, 570
Suzuki, T., 570
Svaeren, S. E., 645
Sval, V. K., 77
Svares, E., 158
Svarichevskaya, S. I., 173
Svechnikov, V. N., 429
Sverdlov, L. M., 296
Svestka, M., 196
Svetlanov, E. B., 257
Sviderskava, Z. A., 78
Svirmickas, A., 681
Svodboda, J. J., 663
Swartz, W.E., 308, 503
Sweeny, J. G., 282, 446
Swenson, J. R., 260,444
Swinglar, D. L., 406
Switalski, J. D., 431
Sworski, T. J., 458
Sydykova, S. S., 413
Symonds, P., 452
Symons, M. C. R., 288,
487, 499, 504, 566, 569,
596, 619
Syrkin, L. N., 554
Syrkin, V. G., 392
Author Index
Syryczynska, B., 82
Sytilin, M. S., 289
Szabo, Z. G., 15
Szepan, R., 198
Szil, Z., 217
Taarit, Y. B., 346, 562,
567
Tabayashi, K., 282
Tabereaux, A., 121, 388
Tachikawa, E., 244
Tada, A., 520
Taddei, F., 359
Taillandier, E., 143, 443
Taira, Z., 168
Tait, J. C., 592
Takacs, G. A., 562, 671
Takagi, K., 462
Takahashi, M., 6, 258,445
Takahashi, Y., 153, 197,
24 1
Takano, T., 394
Takao, S., 452
Takashashi, T., 75
Takashima, M., 232, 238,
654
Takeda, H., 337
Takenaka, H., 232,238,
654
Takeuchi, K., 452
Takeuchi, T., 249
Takeyama, K., 547
Takezawa, S., 607
Takita, Y., 423
Talanova, L. I., 69, 194
Talvidis, N. M., 619
Tamao, K., 292
Tamhina, B., 199
Tamm, N. S., 75, 76, 100
Tamura, K., 240
Tamura, M., 615
Tamura, N., 258
Tan, H. W., 516
Tan, H.-S., 453
Tan, K. H., 205
Tan, L. Y., 252
Tanabe, K., 274
Tanaka, K., 372, 566
Tanaka, M., 203,270
Tanaka, T., 312, 369,372
Tananaev, I. U., 209,
521, 527, 528, 629, 630
Tandon, J. P., 182, 367
Tang, R., 581
Tang, S. P., 441
Tang, S. Y., 250
Tang, Y.N., 402
Tani, H., 186
Tanner, G. T., 211
Tapper, S. R., 205
Taqui Kham, M. M., 526
Tarasenkova, 0. KS., 351
Tarasevich, S. A,, 545,

628
Tarashchan, A, N., 575
Taraskin, S. A., 584
Tarasov, A. A., 34
Tarasov, V. V., 328
Tarasova, A. I., 200
Tarbell, D. S., 364
Tarkovskaya, I. A., 231
Tarnorutskii, M. M., 88,
438
Tarradellas, J., 280, 607
Tartakovskii, V. A., 159
Tarte, P., 202, 326, 327,
352
Tatarinov, V. A., 19
Tatarintseva, M. I., 328
Taube, H., 273, 564
Taubert, R., 96, 97, 444
Taugbol, K., 303
Tavadze, F., 103
Tawaka, K., 249
Taylor, D., 263
Taylor, G. W., 267
Taylor, H. F. W., 331
Taylor, J. C., 406
Taylor, J. K., 282
Taylor, J. W., 560
Taylor, M.J., 205
Taylor, M. W., 494
Taylor, N. J., 485
Taylor, R. S., 524
Tcheichvili, L., 353
Tebbe, F. N., 177
Tebbe, K.-F., 479
Tebiev, A. K., 69, 557
Tedenac, J. C., 74
Teder, A., 616
Tedesco, P. H., 186
Tegman, R., 9, 10, 577
Tehan, F. J., 21
Teichner, S. J., 184, 268
Tejeda, J., 78
Tejwani, G. D. T., 607
Tel, L. M., 256, 494
Telegin, G. F., 508
Telegina, N. P., 355
Telepneva, A. E., 18
Tellgren, R., 56, 631
Tellier, J.-C., 202
Temme, F. P., 175, 667
Temple, R. B., 63, 609
Templeton, D. H., 85,
86, 679
Tench, A. J., 324, 566
Tenygl, J., 560
Teo, W. K., 413, 579
Tepikin, V. E., 339
Terao, N., 236
Terenina, M. B., 515
Ter-Gruft, J. W., 339
Terlecki-Baricevec, A., 434
Author Index
Terras, G., 45
Tertykh, V. A., 318, 321
Terzi, M., 60
Teske, K., 157
Teste De Sagey, G., 603
Teterin, E. G., 276, 515,
542
Tevault, D. E., 48, 51, 453
Thewalt, U., 89
Thakur, C. P., 530
Thalacker, R., 495
Thamm, H., 506
Theobald, H., 307, 441
Therasse, M., 523
Thibault, J., 247
Thiebault, A., 574
Thiele, G., 218
Thielemann, L., 442, 497
Thiery, J. M., 82
Thomas, C. H., 253
Thomas, D., 558
Thomas, H. E., 171
Thomas, J., 433
Thomas, J. M., 233
Thomas, K. M., 253, 505
Thomas, R. K., 261, 674
Thomas, S. G., 261
Thomas, T. D., 39, 482,
591, 658
Thommarson, R. L., 669
Thompson, D. W., 312
Thompson, H., 261
Thompson, J. C., 404
Thompson, J. W., 150,
474,534
Thompson, K. R.,183
Thompson, L. K., 394
Thompson, M., 39, 635
Thompson, R. A., 335
Thompson, R. C., 668
Thomson, C.. 103, 147,
447,464
Thomzik, M., 485
Thornton, S. A., 438
Thrush, B. A., 261
Thulstrup, E. W., 454
Thuraisangham, R., 21 1
Thynne, J. C. J., 258,
307, 473, 501, 622
Tiedemann, P. W., 676
Tiemann, E., 194, 198
Tiernan, T. O., 274
Tigelar, H. L., 265
Tikavyi, V. F., 192
Tikhomirov, ha. V., 297
Tillinger, M., 58
Tillmanns, E., 524
Timms, P. L., 147, 452
Timofeeva, N. P., 356
Timoshenko, Yu. M., 19
Tischer, R., 223
Tischer, R. P., 9
721
Tishura, T. A., 68
Titov, A. P., 46, 327
Titov, L. V., 196
Titov, V. A., 492
Titova, A. G., 155
Titova, K. B., 150
Titova, K. V., 43
Titova, N. S., 133
Tittle, B., 534
Tkacheva, Z. S., 187, 339
Tkhiletkhy, C., 610
Tobias, R. S., 360
Tobias, R. S., 360
Tobisch, J., 79
Toby, S., 261
Todd, L. J., 116, 117,
131, 135, 421
Todd, S. M., 509
Topelmann, W., 501
Torring, T., 194, 198
Tokareva, S. A., 37
Tokuda, M., 516
Tokuda, T., 297
Tokura, N., 551, 607
Tolmachev, S. M., 45,
155
Tolmacheva, L. N., 92
Tolpin, E. I., 116, 133
Tolstaya, T. P., 408
Toma, F., 82
Tomashevskaya, A. N.,
23 1
Tomiie, Y.,248
Tomita, I., 522
Tomlinson, A. J., 485,
489
Tomlinson, C. H., 452
Tomlinson, L., 638
Tomlinson, R. D., 625
Tonev, A., 422
Tong, C. C., 305
Topchieva, K. V., 346
Topchyan, L. S., 429
Tordjman, I., 525, 526,
527
Torikai, E., 353
Torkar, K., 188
Torrie, B. H., 632
Tosatti, E., 148
Tossell, J. A., 316
Tossidis, I., 151, 278,
531, 626
Toth, L. M., 65
Toth, R. A., 260, 463
Touboul, M., 218
TournC, C. M., 519
Tourn6, G. F., 519
Tournoux, M., 220, 222,
521
Touzain, P., 56
Tovbis, A. B., 632
Townsend, L. W., 659
Townsend, R. P., 345

Townsend, W. P., 353
Toyama, H., 570
Tozain, P., 37
Traber, D. G., 24
Traeger, J. C., 243, 297,
436
Traficante, D. D., 107
Trailina, E. P., 201
Tranquard, A., 221
Tranqui, D., 74, 528
Tranchant, J., 45, 46, 176
Traven, V. F., 197, 385
Travena, 1. C., 405
Treichel, P. M., 486
Treiner, C., 17, 460
Tremblay, J., 595
Tremillon, B., 68
Trenafelov, D., 189, 614
Trendovatskii, P. I., 19
Tressaud, A., 194
Tretjakov, I. I., 268
Tretyakov, Yu. D., 202
Tretyakova, K. V., 537
Trheger, J. C., 589
Triche, C., 669
Trichet, L., 20
Tricker, M., 39
Tricker, M. J., 548
Trickey, S. B., 679
Tridot, G., 558
Trifonov, I. I., 71
Trindle, C., 38, 439, 561
Troe, J., 445,463
Tromel, M., 409, 667
Trombe, J.-C., 523, 562
Trotter, J., 200, 474, 507,
511, 600
Trueman, S. P., 590
Trusov, V. I., 492
Truter, M. R., 25, 29,
219
Tsagaireshvili, G., 103
Tsai, B. P., 246
Tsarev, V. S., 531
Tscholakowa, J., 657
Tschudinowa, N. N., 528
Tschuikow-Roux, E., 464,
465
Tselik, E. I., 100
Tselik, I. N., 279, 281
Tsentovskii, V. M., 536
Tsentsiper, A. B., 37
Tserekova, A. M., 635
Tsiklauri, Ts. G., 71
Tsintsadze, G. V., 287,
617
Tsipis, C. A., 544
Tsitsishvili, G. V., 341
Tsivadze, A. Yu., 287, 617
Tskhai, V. A., 236
Tsoneva, R. A., 540
Author Index
722
Tsuda, T., 274
Tsuhako, M., 192, 525,526
Tsurugi, J., 530
Tsvetkov, V. P., 565
Tsvetkov, Yu. V., 350,557
Tsyganok, L. P., 518
Tsyganova, P. S., 641
Tubokawa, N., 231
Tuck, D. G., 208, 211,
214,215
Tucker, P. A., 504, 51 1
Tudo, J., 219
Tukovic, A., 236, 468
Tunaboghi, K., 211
Tunk, T. A., 336
Tupchauskas, A. P., 132,
388
Turetskaya, R. A., 298
Turgunbekova, R., 18,289
Turkevich, A. L., 316
Turner, A. G., 522
Turner, J. B., 296
Turner, R. M., 293
Turnipseed, C. D., 393
Turpin, R., 493
Turq, P., 16
Turyan, Ya. I., 209
Tuttle, T. R., 21
Tuvaeva, T. N., 69
Tykva, R., 225
Tyler, B. J., 454
Tyler, J. K., 446
Tysseland, N., 645
Tzschach, A., 361, 534
Uchida, T., 385
Uchtman, V. A., 92
Udovichenko, L. V., 310
Udupa, M. R., 644,647
Ueda, J., 199
Ueda, S., 468
Ueno, A., 188
Ueo, K., 424
Ugai, V. A., 557
Ugarov, V. V., 612
Ugi, I., 516
Ugulava, M. M., 535
Uhlig, E., 398
Ulbrich, H., 337
Ullmann, R., 140
Ulrich, S. E., 306
Umapathy, P., 77
Umeno, M., 292
Uminskii, A. A., 240
Ummat, P. K., 538
Uncuta, C., 77
Unger, I., 162
Ungurenasu, C., 393
Unland, M. L., 453
Urch, D. S., 82, 174, 588
Uriarte, A. K., 140
Urnes, S., 187
Usanovich, M. I., 315

Ushakov, Yu. V., 19,613
Ushakova, N. I., 209
Uspenskaya, K. S., 227
Ustimovich, A. B., 522
Ustynyuk, Yu. A., 132,388
Utkina, 0. N., 611
Uvedenskaya, T. S., 595
Uytterhoeven, J. B., 318,
341, 346
Uznanski, B., 531
Vaclava, V., 611
Vadasdi, K., 536
Vahrenkamp, H., 140
Vaiciuliene, O., 636
Vaidya, M. C., 278
Vaidya, 0. C., 534
Vainer, L. S., 649
Vaisfeld, M. I., 613
Vakhobov, A. V., 86,
95, 96,648
Valade, J., 360
Valakh, M. Ya., 582
Valetskii, P. M., 139
Valind, S., 10, 92
Valle, B. D., 547
Vallejos, A., 583
Vallet, C., 461
Valpertz, H. W., 532
Van Ausdal, R., 212
Van Bolhuis, F., 602
Van Broekhoven, J. A.
M., 25
Van Brunt, R. J., 267, 272
Van Cauwelaert, F. H.,
318, 346
Vance, T. B., 342
Van de Grampel, J. C., 513
Vandenbulke, L., 236
Van Den Ende, A., 252
Van Der Gen, A., 363
Van Der Griend, L. J., 517
Van Der Hurk, J., 89
Van Der Kelen, G. P.,
307, 535
Van Der Kerk, G. J.
M., 399
Van Der Poorten, H., 589
Vandersall, H. L., 500
Vanderspurt, T. H., 678
Van Der Veen, M., 516
Vander Voet, A., 432
Van De Velde, G. M. H.,
409
Van De Vondel, D. F., 307
Van Deventer, E. H., 50
Van Doorn, J. A., 549
Van Doorne, W., 146, 471
Van Dorpe, B., 203
Vandrish, G., 628
Vangelisti, R., 241
Van Haute, A. A., 654

Van Hook, W. A., 569
Van Paaschen, J. M., 142
Vansant, E. F., 346
Van Schalkwyk, G. J., 483
Van Wazer, J. R., 39,
424, 469, 481, 495,
509, 514, 517, 546
Van Woerkom, P. C. M.,
247
Vardhan, Y.,
231
Varentsova, V. I., 216
Varfolomeev, M. B., 44
Vargas, J. I., 629
Varma, S., 325
Varma, S. P., 418, 449
Varnin, V. P., 227
Vasile, M. J., 549
Vasilenko, N. G., 355
Vasilev, L. N., 580
Vasilev, V. G., 75, 611
Vasilev, V. P., 301, 552,
556
Vasileva, G. A., 389
Vasileva, I. G., 468
Vasileva, N. P., 182, 206
Vasileva, S. I., 461
Vasileva, V. N., 301
Vasilkova, I. V., 71
Vasilos, T., 81
Vasilyanova, L. V., 315
Vaslow, E., 14
Vassbotn, P., 168, 605
Vasserman, I. M., 317
Vasudev, P., 636
Vasyuta, Yu. V., 350
Vaughan, D. J., 316
Vavilova, I. P., 43
Vecher, A. A., 427, 429
Ved, E. I., 188
Vedel, J., 68
Vedrine, J. C., 271, 346
Veillard, A., 482
Veisse, G., 67
Vekshina, N. V., 174
Velichko, I. A., 632
VeljkoviC, S., 184
Venkatachelam, C. R., 134
Venkatakrishnan, V., 156
Venturello, G., 184
Veprek-Siska, J., 442
Veracini, C. A., 655
Verbaere, A., 222
Verchier, P., 200
Verdier, P., 88
Verdonck, L., 535
Verdonk, A. H., 34
Vereshchagin, L. F.,
227,425
Vereshchagina, V. I., 19,
68
Vergnoux, A. M., 34
Author Index
Verkade, J. G., 471, 498,
516, 517
Verma, K. K., 307

Verma, R. K., 622
Verma, V. K., 315
Vermaas, A., 499
Vermeil, C., 435
Vermot-Gaud-Daniel, F.,
51, 584,586
Vershinina, I. I., 276

Verstegen, J. M. P. J., 339
Vertes, A., 306
Vertiprakhov, A. V., 224
Vervaeke, R., 533
Vesper, J., 475
Vevere, I., 77
Viallatte, B., 174
Viard, B., 455
Vicat, J., 74, 329
Vicedomi, M., 422
Vickerman, J. C., 344
Vidal, B., 150
Vielhaber, E., 56
Viennot, J.-P., 253
Vierling, F., 421
Vigdorovich, V. N., 95,
96, 358
Vikane, O., 539, 543

Viktorovskii, I. V., 587
Vilcu, R., 18,62,459,669
Vilkov, L. V., 121, 254
Villa, A., 258, 445, 464
Villa, A. E., 268
Villa, F., 648
Villaume, J. E., 226
Villemin, M., 82
Villermaux, S., 17
Vilminot, G., 490
Viltange, M., 50
Vincent, H., 528,580
Vincent-Forat, C., 528,580
Vincon, G., 367
Vinland, M. L., 270
Vinogradov, E. E., 18,667
Vinogradov, L. I., 309
Vinogradova, L. E., 137
Vinogradova, S. M., 139
Vinokurov, V. M., 352
Vinson, J.-M., 554
Virmani, V. P., 229
Vissers, D. R., 6
Viset, P., 201
Vix, V. A., jun., 497
Vladimiroff, T., 453
Vlasov, V. G., 238
Vlasov, Yu. G., 19
Vlasse, M., 212, 218
Vobecky, M., 59
Vollenkle, H., 56, 333,
365,521, 527, 551
Volter, J., 268

Voet, A., 230, 233
723
Vogt, G. J., 45
VoigtlPnder, W., 534
Voitkiv, V. V., 427, 648
Voitsekhovskii, A. E., 52,
584
Vojtech, O., 613

Volanschi, C., 244
Vol'fkovich, S. I., 158
Volkova, A. N., 321
Volkova, L. A., 352
Volland, B., 532
Volman, D. H., 49, 267,
572
Vol'nov, I. I., 37, 546

Volodin, A. A., 509
Von Barner, J. H., 195
Von-Hartropp, M., 649
Von Hippel, A., 569
Von Niessen, W., 242,
430,438
Von Schenck,
R.,93,
210, 219
Von Schnering, H. G.,

52, 382,467,469
Vorob'ev, G. A., 50
Vorob'eva, L. A., 536
Voronin, G. F., 52, 53
Voronkov, A. A., 327
Voronkov, M. G., 315,361
Voronov, V. A., 193
Voronova, E. M., 519
Vorontsov, E. S., 303
Vorotyagina, V. D., 518
Vos, A., 602
Voskesenskaya, N. R., 527
Votava, I., 194
Vrbenski, J., 193
Vrchlabskf, M., 104
Vrublevskaya, Z. V., 325
VuCeliC, M., 271
Vul', S. P., 427
Vuillard, G., 236
Vvedenskaya, T. S., 303
Vyas, P. C., 526
Vyazankin, G. A., 399
Vyazankin, N. S., 133,
370, 388, 399,401,402
Vyazova, N. G., 79, 351

Vyshinskay, L. I., 389
Wachtel, E. J., 430
Wada, K., 338
Waddington, T. C., 44,
175,484, 667
Wadsworth, W., 516

Wagner, A. J., 504
Wagner, G., 591
Wagner, H. Gg., 440
Wagner, R., 516
Wagner, S.,427
Wagnerova, D. M., 442
Wahlgren, U., 436, 571
Wahner, E., 220, 521

Wakabayashi, A., 249
Wakakuwa, S. T., 207
Wakita, H., 276
Waldman, M. C., 681
Waldron, R. W., 479
Walker, E., 198
Walker, J., 228
Walker, P. L., 232, 590
Walker, R. E., 52
Walker, R. F., 250
Walker, R. W., 452
Walker, W., 469
Wallart, F., 650
Wallbridge, M. G. H.,
112, 114
Wallrafen, F., 71
Wallwork, S. C., 364,
457
Walsh, R., 296

Walsingham, R. W., 401
Walter, E., 159
Walther, B., 529
Walther, D., 398
WanEk, W., 501
Wang, C. H., 248,440
Wang, C. S.-C., 362,
482,618
Wang, F. M., 257

Wang, J. H. S., 247, 257,
261
Wang, J. L.-F., 193, 307

Wang, V. K., 272, 281
Wanmaker, W. L., 339
Wannagat, U., 373, 374,
377, 513
Ward, B., 245

Warkusz, F., 77
Warren, C. H., 261
Warwick, M. E., 268,422
Wasel-Nielen, H.-D., 467
Washburne, S. S., 383
Wasson, J. R., 528
Wasylishen, R. E., 436
Watanabe, I., 263
Watanabe, K., 240
Watanabe, M., 525, 527
Watanabe, N., 232, 238,
654
Watanabe, T., 249

Watanuki, K., 153
Watelle-Marian, G., 570
Water, W. A., 439
Waterworth, L. G., 206,
214
Watkins, J., 46
Watkins, J. J., 293
Watkins, S. F., 395
Watson, R. T., 665
Watson, W. R., 8
Watts, G. B., 514
Watts, J. C., 308
Author Index
724
Watts, P. H., 308
Waugh, J. S., 441
Way, G. M., 131
Wayland, B. B., 314
Weakley, T. J. R., 519
Weaver, J., 397
Weaver, T. R., 398
Webb, G., 591
Webb, T. R., 667
Webber, G. M. B., 12
Webster, D. W., 167
Webster, M., 44, 308,
328,642
Wechsberg, M., 613
Weeks, C. A., 326
Weels, J., 491
Wehrli, F. W., 494
Weibel, A. T., 388
Weichselgartner, H., 2
Weidenborner, J. E., 450
Weidenbruch, M., 384
Weidlein, J., 177, 178,
179, 186,489
Weingand, C., 508
Weinstock, N., 628
Weis, R., 372
Weiss, E., 388
Weiss, J., 644
Weiss, R., 28, 98, 99,
418, 551
Weizer, H., 599
Welch, A. J., 375
Welge, K. H., 562
Wellington, S . L., 26
Wells, E. J., 211
Wells, J. M., 296
Wells, R. L., 144, 374
Welsh, W. A., 308, 642
Weltner, W., 81, 170,
171,237, 578
Wendisch, D., 433
Wendt, H., 557
Wenk, H.-R., 330
Weres, O., 568
Werme, L. O., 436
West, A. R., 47
West, B. O., 389
West, R., 385
West, S. J., 619
Westenberg, A. A., 267,
463, 572
Westerbeck, E., 37
Westerman, P. W., 111
Westheimer, F. H., 517
Westin, L., 78
Weston, A. F., 168, 169
Wexler, S., 561
Whalen, T. J., 9
Wharf, I., 314
Wheatland, D. A., 479
Whiffen, D. H., 282
Whitaker, A., 542
White, A. H., 278

White, D., 436
White, D. W., 471, 517
White, G. L., 182
White, J. M., 258
White, S., 317
Whitehead, H. C., 573
Whitehead, W. D., 267,
272
Whiteley, R. N., 431
Whitesides, G. M., 163
Whitfield, H. J., 543,
545, 582, 627
Whittle, E., 253
Whytock, D. A., 455, 590
Wiberg, N., 80, 164, 383
Wichelhaus, W., 52, 467
Wiebe, H. A,, 258, 445,
464
Wieber, M., 486, 517,
533, 539
Wiech, G., 588
Wiegerink, F. J., 86, 499
Wieghardt, G., 666
Wieker, W., 334
Wiersema, R. J., 131, 134
Wiezer, H., 379, 566
Wilhite, D. L., 296
Wilkinson, G. R., 288
Wilkinson, M., 215
Wilks, J., 228
Willard, J. E., 251, 652
Willett, R. D., 682
Williams, D. A., 505
Williams, D. J., 212,
407, 625
Williams, F., 418, 449,
596
Williams, G. R., 464
Williams, J. K., 487
Williams, J. M., 671
Williams, J. R., 257
Williams, M. B., 102
Williams, P. P., 188
Williams, R. L., 651
Willie, P. J., 187
Willis, C., 268
Willner, H., 278, 629
Willson, W., 242
Wilms, D. A., 654
Wilson, H. W., 287
Wilson, I. B., 490
Wilson, I. L., 200
Wilson, I. R., 289, 439,
617
Wilson, J. W., 152
Wilson. P. W., 406
Wilson, R. D., 259, 538,
651, 658, 659, 664, 677
Wilson, W. I., 337
Wilson, W. W., 661
Winer, A. M., 252
Winfield, J. M., 358,

591, 661
Winkler, C. A., 608

Winkler, F., 460
Winnewisser, G., 247, 606
Winter, C., 233
Witt, J. D., 145, 150,
259, 470,474, 534
Wittez, K., 261
Wittig, G., 8, 560
Wittig, J., 619
Wittmann, A., 56, 333,
350,551
Wittmann, W., 1
Wismar, H. J., 374
Wolke, M., 501
Woerner, V., 666
Wojnowska, W., 370
Wojnowski, W., 370
Wolf, D., 519
Wolf, F., 155, 323
Wolf, R., 498
Wolf, S. N., 296
Wolfe, S.,256, 494
Wolfer, D., 169, 386
Wolff, A., 495
Wolff, H. W., 4
Woltermann, G. M., 528
Wolters, J., 363
Wong, R., 95
Wood, D. J., 7
Wood, E., 394
Wood, R. A., 207
Wood, R. H., 308
Woodhams, F. W. D.,
188,412
Woodruff, W. IT., 652
Woods, M., 506, 507,
511, 530
Woodward, P., 395, 397
Woodward, T. W., 590
Work, R. A., tert., 214,
556
Worms, K.-H., 476
Worrall, I. J., 206, 214,
215
Wrackmeyer, B., 143
Wreford, S. S., 107
Wright, A. F., 317
Wright, J., 116
Wright, J. R., 139
Wright, J. S., 563
Wright, K. J., 465
Wright, R. B., 248, 440
Wroblowa, H. S., 651
Wuensch, B. J., 81, 413,
559
Wyatt, P. A. H., 457
Wykoff, W. R., 5
Yadav, 0. P., 307
Yahagi, M., 11
Author Index
Yajima, S., 171, 173
Yakimov, M. A., 19
Yakovenko, E. I., 61
Yakovlev, L. K., 187,
339, 340
Yakovlev, Yu. B., 218
Yamabe, S., 439
Yamada, H., 203
Yamada, S., 501
Yamada, Y., 274
Yamagata, H., 241
Yamamoto, H., 440
Yamamoto, S., 19
Yamamoto, Y., 364
Yamasaki, A., 315
Yampolskaya, V. V., 531
Yanagida, H., 41
Yanagida, R. Y., 189,
341, 342
Yanaki, A. A., 649
Yanakiev, N. I., 189
Yanik, B., 506
Yano, Y., 244
Yanow, G., 650
Yarandina, V. N., 296
Yarkova, E. G., 309
Yarmolyuk, Ya. P., 198
Yarovoi, A. A., 301
Yarym-Agaev, N. L.,
40,66
Yashimura, M., 551
Yashina, N. S., 314
Yastrebov, V. V., 356
Yasudev, P., 394
Yasumori, I., 423
Yatsenko, S. P., 11
Yatsimirskii, K. B., 522
Yatsurugi, Y., 236
Yeager, E., 61
Yeats, P. A., 365, 366,
614, 661
Yee, K. K., 573
Yeung, E. S., 261
Yoder, C. H., 377
Yogodovskaya, T. V., 563
Yokokawa, T., 155, 318,
575, 628
Yokoyama, Y., 263
Yoshida, A., 191
Yoshida, H., 571
Yoshida, M., 520
Yoshinaga, A.,665
Yoshinaga, N., 338
Young, C. E., 561
Young, H. S., 156
Young, J. F., 335
Young, L. B., 434, 657
Young, R. A., 453, 523
Younger, D., 484
Younglove, B. A,, 650
Yow,H., 676
Yoza, N., 516
725
Ypenburg, J. W., 358,371
Yu, T.-Y., 296
Yuen, G. U., 682
Yui, N., 461
Yupko, L. M., 429
Yurasova, T. I., 678
Yurchenko, V. O., 43, 156
Yuzhelevskii, Yu. A.,
355, 356
Yuzvack, V. I., 629
Yvon, K., 532
Zabdyr, L., 427
Zaborowski, L. M., 465
Zabrodin, I. N., 192
Zacharov, D. M., 429
Zachernyuk, A. B., 355
Zagalskaya, Yu. G., 583
Zagarova, S. A., 354
Zagetova, R. G., 309
Zagidullina, D. Sh., 536
Zagorodnyuk, A. V., 408
Zagorov, S. A., 354
Zagurskaya, L. M., 472
Zahradnik, R., 257
Zaidi, S. A. A., 315
Zaika, T. D., 92
Zaitsev, B. E., 182, 206,
209, 350
Zaitsev, P. M., 310
Zaitsev, Yu. A., 637
Zaitseva, L. L., 613
Zakarov, D. M., 427, 429
Zakharkin, L. I., 56, 87,
133, 137, 175, 207, 495
Zakharov, K. S., 472
Zakharov, V. P., 95, 228,
626, 628, 649,
Zaleski, T. A., 455, 590
Zalivina, E. N., 289
Zalkin, A., 85, 86, 592,
661, 677, 678, 679, 681
Zambonin, P. G., 61, 62
Zamyatin, V. M., 427
Zapipov, N. M., 485
Zapolskii, A. K., 191
Zarechnyuk, 0. S., 198
Zaretskii, S. A., 50
Zaripov, N. M., 491
Zarur, G. L., 453
Zavadovskaya, E. K., 40
Zavorueva, G. N., 19
Zavudnik, V. E., 288
Zdanovskii, A. B., 157,
409, 613
Zebreva, A. I., 12
Zeck, 0. F., 402
Zeegers-Huyskens, Th.,
655
Zegarski, B. R., 560
Zelchan, G. I., 361
Zelenetskii, S. N., 509
Zelenev, Yu. V., 139

Zelichenok, S. L., 59
Zeller, E. J., 229
Zeller, M. V., 381, 424
Zemlyanskii, N. I., 529
Zemlyanskii, N. N., 304
Zemnukhova, L. A., 547,
612
Zenaidi, N., 552
Zettlehoyer, A. C., 319
Zezyanov, S. P., 67
Zhambekov, M. I., 53,
581, 584
Zhsmbulova, M. Sh., 181
Zharkov, A. P., 200
Zharnovskaya, L. P., 19,
612
Zhavoronkov, M. N.,
344
Zhdanov, G. S., 288
Zhefuskaya, N. A., 40
Zhelankin, V. I., 184
Zheshutko, V., 506
Zhigach, A. F., 121, 133,
386
Zhigarnovskii, B. M., 71
Zhitkova, T. N., 157,409
Zhogolev, D. A., 14
Zhorov, V. A., 276
Zhubekova, M. N., 133,
495
Zhukhlister, A. P., 325
Zhukova, L. A., 89
Zhulkov, V. I., 64
Zhuravlev, N. N., 11
Zhuravleva, G. S., 638
Zhuravleva, M. P., 158
Ziegler, M. L., 551
Zilberman, P. Ts., 59
Zimakov, I. E., 60
Zimbrick, J. D., 229
Zimina, G. V., 44, 548,
549
Zimmermann, H., 69
Zingaro, R. A., 531, 627
Ziolo, R., 447
Zins, D., 93, 277
Zmii, 0. F., 78, 427
Znamenskaya, A. S., 633
Znamierowska, T., 526
Zolotareva, L. V., 19
Zolotov, Yu. A., 199, 208
Zorin, A. D., 290
Zorin, R. V., 354
Zorn, J. C., 212
Zschunke, A., 361
Zsinka, L., 521
Zubkov, V. I., 297
Zubzanda, O., 230
Zuca, S., 61
Zuchner, K., 568
Zuckerman, J. J., 362,381
Aiithor Index
Zukharev, V. A., 215
Zumbulyadis, N., 480
Zuonkova, Z. V., 288
Zvagolskaya, E. V., 65
Zvarova, T. S., 196

Zverev, V. A., 23
Zviedre, I., 53
Zvyagin, B. B., 325
Zwetanov, K., 422

Zwierzak A., 518
Zwilling, G., 425
Zyryanov. V. G.. 69

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A Specialist Periodical Report

Inorganic Chemistry of the Main-group

A Review of the Literature Published between

The Chemical Society

ISBN :0 85186 762 6

Printed in Northern Ireland at The Universities Press, Belfast.

The Alkali Metals

Alloys and Intermetallic Compounds

Solvation of Alkali-metal Ions

5 Compounds containing Organic Molecules or Complex

Chapter 2 Elements of Group I I

Chapter 3 Elements of Group Ill

General and Analytical

Chapter 4 Elements of Group IV

By P. G. Harrison and P. Hubberstey

Chapter 5 Elements of Group V

By A. Morris and D. 6.Sowerby

Chapter 6 Elements of Group VI

Chapter 7 The Halogens and Hydrogen

Chapter 8 The Noble Gases

2 Argon, Krypton, and Xenon@)

In this chapter individual references which are inter-related are grouped

H. G . Berry, J. L. Subtil, E. H. Pinnington, H. J. Andrae, W. Wittmann, and A.

Inor,oanic Chemistry of the Main-group Elements

The supply of tritium for this process is derived from:

Within this context, the chemical, physical, and thermal properties of

analysing the liquid are obviously important. Photon activation appears

Inorganic Chemistry of the Main-group Elements

L. Minnhagen and H. Nietsche, Physica Scripta, 1972, 5 , 237.

193.6 - 0.094(t - 98)

107.1 - 0.069(t - 64)

The values correlate well with those previously p u b l i ~ h e d . ~ ~

A. N. Solov'ev and A. A. Kiriyanenko, Fiz. Khim. Poverkh. Yavlenii Vys. Temp.

Inorganic Chemistry of the Maimgroup Elements

The enthalpy of formation, AH', of potassium hydride as derived from these

A. K. Fischer, U.S.P. 3 745 068 (CI. 176-38, B O l j , G21c), 10 Jul 1973.

H. U. Borgstedt and G. Frees, Rev. Coatings Corrosion, 1972, 1, 43.

Inorganic Chemistry of the Main-group Elements

from T = 387 to 828 K, using the least-squares method. This equation is

R. L. Klueh, Corrosion (Houstom), 1972, 28, 360.

A technique, reminiscent of the electrochemical oxygen meter, is described,

M. R. Hobdell and D. M. J. Rowe, RD/B/N-2240 Rept. 1972.

Iiiorganic Chemistry of the Main-group Elements

D. G. Oei, Inorg. Chem., 1973, 12,438.

3 Alloys and Intermetallic Compounds

have been determined by using a double-oven technique in combination with

K. Kuriyama, M. Yahagi, and KIwamura, Jap. J. Appl. Phys., 1973,12, 743.

Inorganic Chemistry of the Maingroup Elements

4 Solvation of Alkali-metal Ions

Inorganic Chemistry of the Main-gvoup Elements

using an electrochemical quadruple cell without liquid junction. The value of

Table 1 Valuesof rJA andPaulingcrysta1 radii rc/Afor ions in aqueous solution

A. H. Narten, E. Vaslow, and H. A. Levy, J. Chem. Phys., 1973, 58, 5017.

for comparison, With increasing temperature two phenomena affect hydration

Inorganic Chemistry of the Maingroup Elements

NaClO, are preferentially solvated by water ( @,/axl < 0) whereas NaCIO,

C. Treiner, J. F. Bocquet, and M. Chemla, J. Chim. phys., 1973, 70, 472.

Table 2 Aqueous systems that have been investigated

LiB02-CO (NH 2)2

4Na2S0,,3 CdSO, ,3Hz0

V. G. Skvortsov, Zhur. neorg. Khim., 1973, 18, 243.

Table 2 Aqueous systems that have been investigated

KNOB-CO (NH,),-Cr( N03)3 KNOs,CO(NH2), ;Cr (N03)B,6CO(NHz)21 39