Transition Met. Chem.

, 20, 417 422 (1995)

Double complex salts of cyclic diamine ligands

417

Solid state M6ssbauer, e.p.r., magnetic properties and thermally

induced stereochemical studies on double complex salts of cyclic
diamine containing cationic copper(II) complexes and a hexacyanoferrate(III) anion
Parimal Kundu and Samiran Mitra*
Department of Chemistry, Jadavpur University, Calcutta 700 032, India
Sonjay Kumar, Dilip Banerjee and Ranga Lal Bhattaeharya
Department of Physics, Calcutta University, 92 Acharya PrafulIa Chandra Road, Calcutta 700 009, India

Summary
Double complex salts containing cationic Cu n having
cyclic ligand piperazine (pipz), N-methylpiperazine
(mpipz) and N,N'-dimethylpiperazine (dmpipz) and hexacyanoferrate(III) ion have been synthesized and characterized by elemental analyses, i.r. and electronic spectra,
and magnetic moment measurements. M6ssbauer spectra
at room temperature and at 80 K, were recorded in order
to evaluate the metal-metal charge transfer and the
impact of the cyclic ligand present in cationic moiety of
the double complex salt upon the M6ssbauer spectra of
the hexacyanoferrate(III) ion. Evidence for metal-metal
charge transfer is supported by electronic spectra and
magnetic susceptibilities. Variable temperature e.p.r.
spectra were recorded in order to determine the distortion
of crystal system. Thermally induced stereochemical studies have been carried out with the help of i.r. spectral
data. Kinetics of thermochemical reactions have also been
studied. Activation energies (E*) and inception temperatures for the thermochemical reactions show the order of
stability of the double complex salts follows the trend:
dmpipz > mpipz > pipz, which indicates that the + I effect is more pronounced than steric effect.

Introduction
Studies of double complex salts and cyanide-bridged
complexes containing cationic metal(II/III) complexes
and hexacyanoferrate(III/II) ions are of particular interest
in connection with electron transfer phenomena in the
solid state. Unfortunately, well characterized complexes
have not been reported, excepting those containing
cationic ruthenium(III) (1) and manganese(II) (2)complexes
as a counter ion. Further studies are needed for advanced
elucidation of electron transfer reactions of metal complexes in the solid state. Suzuki and Uehara et al. ~3) have
studied thermal and electronic properties of double complex salts and cyanide-bridged complexes containing
cationic copper(II) complexes with an acyclic diamine
ligand and a hexacyanoferrate(II) ion. These authors cited
charge transfers from iron(II) to copper(II), the stability of
the [Cu(L2)] 2+ moiety decreasing due to the influence of
the Fe(CN)64- ion. The aim of the present work was to
prepare double complex salts and cyanide-bridged complexes containing cationic copper(II) having a cyclic
ligand and a hexacyanoferrate(III) ion, in order to observe

* Author to whom all correspondenceshould be directed.

0340 4285 9 1995 Chapman& Hall

the charge transfer phenomena and the effect of the

Fe(CN)63- ion on the stability of copper(II) complexes
containing cyclic ligands.
Structural and M6ssbauer spectral studies on Prussian
blue-type complexes have been reported ~-8) but no M6ssbauer study has been made on the double complex salt
containing the copper(II) cation cyclic ligand and hexacyanoferrate(III). Thus, a further purpose of the present
work was to study M6ssbauer spectra and to interpret the
difference in spectral parameters from the Cu 3[Fe(CN)6 ] 2
due to the presence of the cyclic ligand in the cationic
copper(II) unit. Attempts have also been made to draw
conclusions as to the distortion of the crystal due to
insertion of the cyclic ligand in the cationic moiety of
the complexes, from the temperature-dependent e.p.r.
spectra(9-1 ~.
Although thermally-induced stereochemical changes of
cyclic ligand complexes in the solid state have been reported (~2'13), this is not the case for the double complex
salts. One purpose of the present work is to study
stereochemical changes during thermal decomposition.
Kinetics and thermodynamic parameters for the dehydration and decomposition in the solid state have been
calculated. The stability order of the complexes with
respect to methyl substitution in the cyclic ligand are also
discussed.

Experimental
Materials and methods
Metal salts (A.R. grade) were used as received. Pipz (S.D.
fine chemicals, Calcutta), mpipz (Spectrochem, Bombay)
and dmpipz (Aldrich Co., USA) were used as supplied.

Preparation of the complexes

The ligand (pipz, mpipz or dmpipz) was added in excess,
with constant stirring, to an aqueous solution (30cm 3)
containing CuC1 z (ca 3 retool) until the solution became
clear. An aqueous solution of K3[Fe(CN)6 ] (30cm 3,
2retool) was then added with constant stirring and the
solution became purple. The complex was precipitated by
adding M%CO and was collected by filtration, washed
carefully with cold H 2 0 and dry Et20 and dried over
fused CaC12 in a desiccator. (Yield ca 60%). The complexes have the composition [-CuL2][L2CuCNFe(CN)512"nHzO , where L=pipz, mpipz or dmpipz and
n=5or6.

418

Kundu et al.

Transition Met. Chem., 20, 417-422 (1995)

Table 1. Analytical data for the double complex salts

Compound a

Colour

(I)

maroon

(2)

purple

(3)

purple

Found (Calcd.)(%)
C
N

Cu

Fe

35.3
(35.4)
38.3
(38.1)
41.1
(41.0)

5.4
(5.7)
6.2
(6.3)
6.6
(6.8)

15.5
(15.6)
14.3
(14.4)
13.5
(13.5)

9.1
(9.1)
8.3
(8.4)
7.9
(719)

27.0
(27.5)
25.3
(25.4)
23.7
(23.9)

"(1) [CuL]][L1,CuCNFe(CN)5]2.5H20;

(2) [CuL~][L~CuCNFe(CN)s]2.6H20;
L 2 = N-methylpi'perazine and L 3 = N,N'-dimethylpiperazine.

C, H, N were estimated using a Perkin-Elmer 240 C

elemental analyser; elemental analyses are given in
Table 1. Thermal investigations (t.g,a. and d.t.a.) were
carried out on a Shimadzu DT-50 thermal analyser under
a N 2 atmosphere with a heating rate of 10 ~ min- 1 and
c~-alumina as a standard. I.r. spectra were recorded using
a Perkin-Elmer 595 Spectrometer with KBr discs. The
effective magnetic moments were evaluated from magnetic susceptibility measurements with an E G & G PAR 155
vibrating sample magnetometer at room temperature.
Variable temperature magnetic measurements were carried out with a Faraday type magnetometer (Manics
DSMB) equipped with an Oxford He continuous-flow
cryostat working in the 4.2-300 K range, and a Drusch
EAF 16UE electromagnet. Solid state electronic spectra
were recorded using Hitachi U-3400 (u.v.-vis.- near-i.r.)
model electronic spectrophotometer. E.p.r. spectra were
recorded at 4, 77 and 298 K with a Bruker-190 spectrometer equipped with a continuous flow cryostat, s 7Fe M6ssbauer spectra were obtained using a C M T E constant,
acceleration drive (Model 250) with ca 5 mci 57Co in Pd as
source. The transmission spectra were obtained using
ECIL krypton-methane filled proportional counter and
associated components to limit detection to only
14.37 KeV y-ray. The transmitted radiation was registered
in a 4 K PCA card in multiscalar (MCS) mode. The spectra
were recorded at 300 and 80 K.

Results and discussion

Analytical data, colour and magnetic moments for the
three new double complex salts, ( I ) - ( 3 ) , are given in the
Table 1. The presence of lattice water molecules in the
double complex salts was confirmed by the presence of i.r.
bands at ca 3600 cm- 1, y(OH), and at 1650 cm- 1, 6(HOH).
I.r. bands are listed in Table 2A. On heating, the compounds lost water. Mass loss in t.g.a, curves confirmed the
presence of five molecules of water in (1) and six molecules
of water in (2) and (3) (Figure 1, Table 3).
In the complexes the cyclic ligands function as a chelate
in the boat conformation, as shown by the appearance
of additional i.r. bands between 700 and 1400cm -1
(Table 2A) compared with the free ligand which exists in
the chair form ~12-17). From the i.r. spectral bands it is
inferred that both terminal and bridging cyanides are
present in the complexest18'19). The ?(CN) and 6(CN)
values are given in Table 2A. I.r. spectral bands for y(CN)
appeared at lower frequenc!es than in K3[Fe(CN)6], indicating that the charge on iron(III) reduced to some extent
in complexes ( I ) - ( 3 ) ; i.e. charge transfer phenomena are

Pefr
(B.M.)
3.74
3.69
3.55

(3) [CuL,3][L~CuCNFe(CN)5]2.6HzO;

L'=piperazine,

170"C

~ "~,---...~(3) 125"oc

'" 140~C

\ TO ~ " - - ~ 1 8 5 ' 0 C

115~
.~ TG " ' 4 - 4 - , 1 7 5 a 0
LG

\ ~

//~

\
,,
t 11

7"

/
-~o--c . . . .
!
,,/

/"
~ , . - ....... j . "
~

~. '(31
I/.' DTA

I(2)
'hi DTA

2.5.__
mgj
20 ~V

J_

Figure 1. Thermal curves of compound (1) (

), sample
mass 18.10mg; (2) (
), sample mass 14.00mg; and (3)
(. . . .

), sample mass 9.22 mg.

present in the complexes. This fact is supported by electronic and M6ssbauer spectra and magnetic moments.
The electronic spectra of all the double complex salts
were recorded in the solid state and are shown in Figure 2.
An extra band (shoulder) appeared at 1065 nm in all the
complexes which was not observed in the individual double
complex salts. This extra band appeared to be due to
metal-metal charge transfer ~3).
M6ssbauer spectra of the compounds were recorded
and are shown in Figure 3. The isomer shift (6, IS) and
quadrupole splitting (A, QS) values (Table 4) were determined by a computer curve-fit program ~2~ and are expressed in mm s- 1. For complexes ( 1 ) - ( 3 ) the 6(mm s- a)
values are close to zero and quadrupole splittings (A) are
zero. So instead of obtaining the characteristic quadrupole
splittings and isomer shifts for hexacyanoferrate(III)
the spectra indicated the presence of hexacyanoferrate(II)
but no detectable hexacyanoferrate(III) at room temperature. The line widths at half-height (F/2) of all three complexes are appreciably large. The M6ssbauer spectra for
complex (1) at 80K contains one quadrupole doublet

3605vs
3470s
3275sh
3215s

3500sbr
3300s

3600vvs
3470s
3260sh

(1)

(2)

(3)

2980ms
2940w
2880w

3100ms
2980sh

2950w
2920vvw
2850vw
2840vw

7(CH2)

2098vs
2073vs

2100vvs
2078vs

2110vs
2085vs

y(CN)

1680sh
1640sh
1600s

1660sh
1650vs

1650sh
1640sh
1600vs

6(NH) + 6(HOH)

1520ms
1480s
1440ms

1500ms
1480ms
1450sh
1400ms

1450s
1435s
1415s

6(CHJ

1370ms
1340sh

1390vw
1365w
1355ms

1390sh
1365ms

pw(CH2)

2950w
2920vw
2850vw

3100ms
2960sh

2980ms
2940w

3605vs
3470s
3275sh

3500sbr
3300s

3600vs
3470s
3240vs

(isolated
at 240 ~

(isolated
at 260 ~

(3a)

(isolated
at 220 ~

(2a)

(la)

7(CH2)

7(NH)

Intermediate product

2098vs
2073ms

2100vs
2078vs

2110vs
2085vs

7(CN)

1680sh
1600s

1660sh
1650s

1650sh
1640sh

6(NH)

1520ms
1480s
1435s

1500ms
1480ms
1450sh
1395ms

1450s
1435s
1415s

6(CH2)

1360ms

1355ms

1365s

1320ms
1300vw

1330w

1325ms

r(NH) + p~(NH) +

1320ms
1300vw

1330w
1300vw

1330sh
1325ms
1295ms

"c(CH2)

z(NH) + p~(NH) + z(CH2)

Pw(CHj

Table 2B. I.r. spectral data (cm ~) of the intermediate product of the double complex salts

y(NH) + y(OH)

Complex

Table 2A. l.r. spectral data (cm a) for the double complex salts

1170ms
1115s
1085ms
1060sh
1020s
1220s
1180ms
1120ms
1100s
1010s
1210ms
1180s
1080ms
1020ms

7(CN)+7(C

1205w
1170ms
1115s
1085s
1070sh
1040s
1000sh
980w
1220ms
1180s
1120ms
1100s
1080s
1030sh
1010vs
990sh
970vvw
1250w
1210ms
l180s
1120vs
1090vs
1080sh
1050w
1020vs
1010sh

7(CN) + 7(C---C)

C)

890vs
880sh
815w
660w

900s
880vs
870w
805vvw
770vw
680sh

885vs
880s
810w

890vs
880sh
660w

900s
880s
870w
670sh

880vs
875s

p~(CH2)

p~(CH2) + pe(HOH)

600sh
580vs

580s

570vs

y(M

600sh
580vs

580vs

575vs

N)

y(M---N)

565s

430w
405w

470ms
400s

6(MCN)

465s

430w
400w

480ms
410ms

6(MCN)

~=~
"~

~"

~"

t~

t~

cr

MD

4~
b..)

b,J

t%

Kundu et al.

420

Transition Met. Chem., 20, 417-422 (1995)

Table 3. Thermal parameters for the dehydration and deligation of double complex salts
Dehydration process
Temp.
d.t.a, peak
range (~
temp. (~
(Endo.)

Order of
reaction

E*
(k~Jmol- 1)

Deligation process
Temp.
d.t.a, peak
range (~
temp. (~
(Endo:)

Order of
reaction

E*
(kJ mol- 1)

(I)

35-75

45

2.0

173

170-250

1.5

170

(2)
(3)

40-115
35-125

80
82

1.8
1.8

165
164

175-255
185-280

1.5
1.5

176
181

Compounds

190,220,
240
180,220
190,260

Table 4. M6ssbauer parameters for double complex salts

1.o

Compound

1"/2
(mm s- ~)

(mms -1)

Quadrupole
splitting
(mms -1)

+0.0076
+ 0.0232
+0.0121
- 0.1800
+ 0.0400
-0.1240

0
0
0
0.400
0
0.280

0.38
0.40
0.39

Isomer
shift a'b

(I)
(2)
(3)
Cu 3[Fe(CN)6] ~
K4[Fe(CN)6] c
K3 [Fe(CN)6] c

305 -

aRelative to or-iron;bvelocity scale is calibrated by S~Co Pd source and

ct-Fe and ct-Fe203 absorbers; CRef. 8.
0 ~ . l
200

t
I
I
600
1000
Wavelength (nm)

_~

I
1400

Figure2. Electronic spectra in Nujol mull of compound (1)

), (2) (- --) and (3) (. . . . . ).

16.00

...

1 9
"~-[

(1

/
9

(2)

"

..

15.75
15.50
x 15.25
co

E 15.00
g
9 14.75
(3 11.7~-

14.50

11.51
200

14.25 --I
200
250
300
Channel number
16.9

(3)

9.e

V
1
t
250
Channel number
~

300

',,

~16.6
x
us

9 16.3

(IS = 0.042 mm s- 1; QS = 0.286 mm s- t) and one singlet

(IS = 0.002 mm s- 1; 1"/2 = 0.19 mm s- 1). The small quadrupole splitting of the doublet indicates the presence of
hexacyanoferrate(III) and the singlet corresponds to hexacyanoferrate(II). So, in this compound a certain percentage
of hexacyanoferrate(III) is present which is not observed at
room temperature. From this result it is concluded that
charge transfer occurs in this compound. The value of F/2
decreases with the fall of temperature for hexacyanoferrate(II) which indicates the lowering of distortion of the
system with reduction of temperature (21). With lowering of
temperature the absorption percentage increases which
informed the presence of polymeric lattice. The M6ssbauer
spectral parameters of complexes ( 1 ) - ( 3 ) are different
from C u 3 r F e ( C N ) 6 ] 2 (7'8). C u 3 [ F e ( C N ) 6 ] 2 exhibits a definite quadrupole splitting (A) and isomer shift (Table 4).
This difference arises from the cyclic ligand attached with
the copper(II) ion. The magnetic moments of complexes
( 1 ) - ( 3 ) at room temperature are much lower than the
expected values. Variable temperature magnetic moments
of complex ( I ) (given in Table 5) are almost constant.
Thus, no antiferromagnetic coupling is present in this
compound. Similar phenomena are also observed in complexes (2) and (3). From the above discussions it is
concluded that charge transfer occurs in all the compounds
in the direction: L ~ C u I I ~ Fe m, which is further supported
by the higher thermal stability of cationic copper(II) cyclic
ligand complexes in double complex salts compared to
[ C u L 2 ] X 2 complexes (22'23).

16.0

190

I
i
I
230
270
Channel number

Figure 3. Mrssbauer spectra of compounds (I) and (2). The zero

velocity channel is 247.75 and the velocity is 0.04 mm s- 1 c h a n n e l -1.
Compound (3) has a similar spectrum.

In complex (1) variable temperature e.p.r, spectra have

been recorded in the solid state (Figure 4, Table 6) and an
unusual phenomenon is observed. With the lowering of
temperature, the difference in e.p.r, spectral bands due to
Cu 2 + centres gradually decreases and at 4 K merges to give
one broad peak. From the literature it is known that
Prussian blue analogues have face-centred cubic symmetry.

Transition Met. Chem., 20, 417-422 (1995)

Double complex salts of cyclic diamine ligands

421

Table 5. Variable-temperature magnetic moments of double

complex salt (1)

Table 6. E.p.r. spectral parameters for (1) at different temperatures

Temp.
(K)

/~
(B.M:)

Temp.
(K)

/~
(B.M.)

(K)

5.00
6.99
8.99
10.99
13.00
15.00
17.00
19.00
21.00
23.00
25.09
27.09
29.09
31.10
33.07
35.08
40.06
45.04
50.00
55.00
59.95
64.92

3.159
3.085
3.048
3.030
3.017
3.012
3.009
3.008
3.008
3.009
3.013
3.017
3.021
3.025
3.029
3.033
3.051
3.063
3.072
3.088
3.101
3.114

69.92
74.91
79.88
84.86
89.86
94.83
99.82
109.85
119.81
129.80
139.81
149.73
159.74
169.73
179.68
189.69
199.67
219.71
239.66
259.66
279.60
299.50

3.128
3.143
3.157
3.171
3.185
3.199
3.212
3.240
3.266
3.296
3.322
3.347
3.372
3.398
3.423
3.448
3.471
3.517
3.560
3.599
3.640
3.681

Temp.
298
77
4

gii

g~

gay

2.21
2.20

2.12
2.12
-

2.15
2.15
2.14

ture and tends to a perfect crystal system. Integration of the

e.p.r, spectra indicates that all the copper is present as
copper(II). The g values support the presence of four and
five coordinated copper(II)(24-27).
On heating, all the complexes decompose by dehydration, showing mass loss in t.g.a, curves and endothermic
peaks in d.t.a, curves (Figure 1, Table 3). F o r the decomposition process mass loss in the t.g.a, curve corresponds
to three molecules of cyclic diamine in complexes (1)(3). The intermediate product in each case was isolated
by keeping the rate of heating at 1 ~ in the respective
m a x i m u m decomposition temperature. The i.r. spectra
show that the cyclic diamines in the intermediate complexes exist in the chair form as the number of i.r. active
bands between 700 and 1400 c m - 1 is less than that in the

2. ~

(a)

1000

(b)

2000

3000

I
V

CN

NC
(c)

I
I
I

I
I
I

4000

5000

6000

[G]
Figure 4. E.p.r. spectra of compound (I) at (a) 298 K; (b) 77 K; and
(c) 4 K.

Fe

I
J

I
I

NC .

~.

I
C 84

N
We therefore tentatively conclude from the e.p.r, spectra
that some distortion appears in the anionic part of the
crystal system due to insertion of ligand in the copper(II)
ion which gradually decreases with lowering of tempera-

Figure 5. Proposed structure of the anion.

CN

422

Kundu et al.

boat form (12'14'16) (Table 2B). The activation energy and

order of reaction for the dehydration and decomposition
have been evaluated from the t.g.a, curves using the Coats
and Redfern equation~Za); values are given in Table 3.
Thermal decomposition occurred at the copper centre
without disturbing the hexacyanoferrate(III) ion [i.r.
spectra exhibit 7(CN) after decomposition]. From the
data in Table 3 it is observed that decomposition of the
double complex salts started at higher temperature than
that of copper(II) complexes of the same ligand. This is
due to the presence of the hexacyanoferrate(III) ion as
explained above. Figure 5 shows the proposed structure
of the anion.
Electron release from the methyl group to nitrogen
leads to an increase in stability of the complexes. This
stability also depends upon a steric factor (12'a3'29) which
operates in the opposite direction to + I effect. The stability order (with respect to E* and inception temperature)
of these complexes follows the trend: d m p i p z >
mpipz > pipz. Therefore, the + I effect is more pronounced than the steric effect in the present case.

Acknowledgements
We thank Professor J. Ribas, Department of Inorganic
Chemistry, University of Barcelona, Spain, for e.p.r.
spectra and temperature-variable magnetic susceptibility
measurements. We also thank Professor R. G. Bhattacharyya, Jadavpur University, Calcutta 700 032, India,
for instrumental facilities. Finance of the thermal analyser
(TGA-50, DTA-50) by the DSA fund is gratefully acknowledged. Financial assistance (PK) from CSIR, New
Delhi, India, is also gratefully acknowledged [Grant
01(1249)/92/EMR-II].

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(Received 30 August 1994)

TMC 3355