136 INORGANIC SYNTHESES

The more slowly the cooling process is performed, the larger

the size of the individual crystals.
Tungsten(V1) chloride forms nearly black crystals under
a dark brown solution when the mixture is cooled. As with
molybdenum(V) chloride and niobium(V) chloride, the
size of the crystals may be regulated by controlling the
cooling rate.
The reaction has been found to be unsuitable starting
with the following oxides: Bz03, A1203, Ti02, Zr02, ThO2,
Ta205, c0304, NiO, Fe203, Cr203, Mooz, Mn02, and Sb206.
Properties
The properties of vanadium(II1) chloride,2 niobium(V)
~hl or i de, ~ molybdenum(V) ~hl ori de, ~ and tungsten(V1)
chloride5 have been previously described.
References
1. J. A. HERMANN and J. F. SUTTLE: INORGANIC SYNTHESES, 6, 143 (1957).
2. N. V. SIDGWICK: The Chemical Elements and Their Compounds,
3. K. M. ALEXANDER and F. FAIRBROTHER: J . Chem. SOC., 1949, 233.
4. 0. HONIGSCHMID and G. WITTMAN: 2. Anorg. Allgem. Chem., 229, 65
5. M. H. LIETZKE and M. L. HOLT: INORGANIC SYNTHESES, 3, 163 (1950).
p. 826, Oxford University Press, London, 1950.
(1936).
36. TETRAHALO COMPLEXES OF DIPOSITIVE
METALS IN THE FIRST TRANSITION SERIES
SUBMITTED BY NAIDA s. GILL* AND F. B. TAYLORt
CHECKED BY W. E. HATFIELD,$ W. E. PARKER,$ CAROL S. FOUNTAIN,$
AND FRED L. BUNGER~
Considerable interest attaches to the spectral and mag-
netic properties of the tetrahalo complexes of the first
* Australian National University, Canberra, Australia.
t University College, London, England.
2 University of North Carolina, Chapel Hill, N.C.
Inorganic Syntheses, Volume IX
Edited by S. Young Tyree, Jr.
Copyright 1967 by McGraw-Hill Book Company, Inc.
TETRAHALO COMPLEXES OF DIPOSITIVE METALS 137
transition series elements. In the synthetic methods
described below they are crystallized as salts of large
cations, e.g., tetraethylammonium or triphenylmethylarso-
nium, from weakly coordinating solvents.
A. MANGANESE COMPOUNDS
1. Bis (tetraethylammonium) tetrachloromanganate (11).
Solutions of 1.98 g. of manganese(I1) chloride tetrahydrate
(0.01 mol) and 3,68 g. of tetraethylammonium chloride
monohydrate (0.022 mol) in 10 ml. of hot absolute ethanol
are filtered and mixed, and the mixture is boiled for one
minute. The pale green crystals are collected on a sin-
tered-glass filter and dried in vacuo. Further crystals are
obtained by evaporation of the mother liquor to about
one-half the initial volume. The
deliquescent crystals are recrystallized most conveniently
from a 60 : 40 methanol-absolute ethanol mixture. The
solution is evaporated nearly to dryness to recover the
product. The yield is 3.6 g. (79%). Anal. Calcd. for
[NEt4I2[MnCl4]: C, 42.0; H, 8.8; N, 6.1; C1, 31.0; Mn, 12.0.
Found: C, 42.3; H, 8.8; N, 6.5; C1, 30.9; Mn, 12.2.
2. Bis (tetraethylammonium) tetrabromomanganate (11).
This is prepared in the same way as the chloro compound.
The quantities of reagents used are 1.43 g. MnBr2-4H20
(0.005 mol) in 10 ml. of absolute ethanol and 2.10 g. NEt4Br
(0.01 mol) in 7 ml. of absolute ethanol. The very pale
green crystals are recrystallized from absolute ethanol.
The mother liquor is evaporated further to recover nearly
all the product. The total yield is 2.7 g. (85%). (The
checkers report a 56% yield.) Anal. Calcd. for [NEt4I2-
[MnBr4]: C, 30.3; H, 6.35; N, 4.4; Br, 50.3; Mn, 8.6.
Found: C, 30.9; H, 6.2; N, 4.4; Br, 50.4; Mn, 8.4.
tetraiodomanganate (II) .
It is difficult to crystallize this compound from ethanol
because it is quite soluble in the hot solvent and on cooling
the solution tetraethylammonium iodide is obtained. How-
ever, it is possible to obtain the complex if excess manga-
The yield is nearly 4 g.
3. Bis (tetraethylammonium)
138 INORGANIC SYNTHESES
nese(I1) iodide is used (2 mols to 1 of NEtJ). The solution
is evaporated, and the crystals are filtered from the hot
solution to avoid the crystallization of the ammonium
halide. The best method of preparation uses glacial acetic
acid as solvent. Hot solutions of 0.76 g. of MnIz.4H20
(0.002 mol) in 15 ml. of glacial acetic acid and 1.03 g. of
NEt J (0.004 mol) in 15 ml. of glacial acetic acid are mixed.
The mixture is filtered immediately, and the yellow crystals
are dried in oacuo at room temperature. The crystals
cannot be recrystallized without some decomposition, and
they decompose slowly on keeping. The yield is 1.5 g.
(91%). (The checkers report a 48% yield.) Anal. Calcd.
for [NEt4I2[MnI4]: I, 61.7; Mn, 6.7. Found: I, 61.4;
Mn, 6.7.
B. IRON COMPOUNDS
To prevent oxidation of the iron compounds, they are
prepared in an atmosphere of nitrogen and in ethanol from
which dissolved oxygen is removed by boiling and cooling
under oxygen-free nitrogen.
1. Bis(tetraethy1ammonium) tetrachloroferrate(I1). So-
lutions of 0.81 g. of FeCl2.2H2O1 (0.005 mol) in 5 ml. of
absolute ethanol and 1.84 g. of NEt4C1.H20 (0.01 mol) in
5 ml. of ethanol are filtered separately into flask 1 (Fig. 10)
through the sinter by applying suction at A, the nitrogen
stream through B being disconnected momentarily. The
complex precipitates immediately and is filtered by apply-
ing suction to C. The cream crystals are dried partially
by blowing nitrogen over them while they rest on the glass
sinter. They are dried finally in vacuo at room tempera-
ture. The yield is 1.34 g. (59%). Anal. Calcd. for
[NEt4l2[FeCl4]: C, 41.9; H, 8.8; N, 6.1; C1, 30.9. Found:
C, 41.4; H, 8.9; N, 6.1; C1, 31.3.
2. Bis (tetraethylammonium) tetrabromoferrate (II). This
compound is prepared in the same manner which is used for
the preceding compound using 1.27 g. of FeBrz*2Hz0
(0.005 mol) in 5 ml. of absolute ethanol and 2.10 g. of
TETRAHALO COMPLEXES OF DIPOSITIVE METALS
139
Et4NBr (0.01 mol) in 5 ml. of absolute ethanol as the start-
ing solutions. The yield of pale brown crystals is 1.7 g.
(55%). Anal. Calcd. for [NEt4I2[FeBr4]: C, 30.2; H, 6.4;
N, 4.4; Br, 50.3. Found: C, 30.5; H, 6.1; N, 4.6; Br, 50.5.
FIG. 10.
C. COBALT COMPOUNDS
Tetrahalocobaltate(I1) salts are prepared in a manner
similar to that used for the manganese compounds. The
chloro and bromo derivatives are recrystallized from abso-
lute ethanol, the solutions being evaporated to obtain the
crystals.
1. Bis (tetraethylammonium) tetrachlorocobaltate (11).
Amounts of reagents used are 1.19 g. CoCI2-6H20 (0.005
mol) in 5 ml. of absolute ethanol and 1.84 g . NEt4C1-H20
(0.01 mol) in 5 ml. of absolute ethanol. The yield of blue
crystals is 1.8 g. (79%). Anal. Calcd. for [NEt4]2[CoC14]:
140 INORGANIC SYNTHESES
C, 41.7; H, 8.7; N, 6.1; C1, 30.7. Found: C, 42.2; H, 8.5;
N, 5.8; C1, 30.1.
2. Bis(tetraethy1ammonium) tetrabromocobaltate(I1).
Amounts of reagents used are 1.63 g. CoBr2-6H20 (0.005
mol) in 5 ml. of absolute ethanol and 2.10 g. NEt4Br (0.01
mol) in 5 ml. of absolute ethanol. The yield of pale blue
crystals is 2.5 g. (80%). (The checkers report 62% yield.)
Anal. Calcd. for [NEt4I2[CoBr4]: C, 30.1; H, 6.3; N, 4.4;
Br, 50.0. Found: C, 30.1; H, 6.4; N, 4.3; Br, 50.6.
3. Bis(tetraethy1ammonium) tetraiodocobaltate (11).
The best solvent for this preparation is glacial acetic acid.
Amounts of reagents used are 2.10 g. Co12.6H20 (0.005 mol)
in 15 ml. acetic acid and 2.5 g. NEt41 (0.01 mol) in 15 ml.
acetic acid. The yield of green crystals is 3.2 g. (77%).
Anal. Calcd. for [NEt4I2[CoI4]: C, 23.2; H, 4.9; I, 61.4.
Found: C, 23.1; H, 4.9; I, 61.4.
D. NICKEL COMPOUNDS
The chloro and bromo compounds are prepared in the
same way as the analogous manganese and cobalt com-
pounds, and again the solutions must be evaporated to
obtain reasonable yields.
1. Bis (tetrae thylammonium) tetrachloronickelate (11).
Amounts of reagents used are 1.19 g. NiCl2*6H20 (0.005
mol) in 10 ml. of absolute ethanol and 1.84 g. NEt4C1-H20
(0.01 mol) in 5 ml. of absolute ethanol. The yield of blue
hygroscopic crystals is 1.85 g. (65%). Anal. Calcd. for
[NEt4I2[NiCl4]: C, 41.7; H, 8.7; C1, 30.8; Ni, 12.7. Found:
C, 41.8; H, 8.9; C1, 30.7; Ni, 12.9.
2. Bis (tetraethylammonium) tetrabromonickelate(I1).
Amounts of reagents used are 1.36 g. NiBrz.3H20 (0.005
mol) in 8 ml. of absolute ethanol and 2.10 g. NEt4Br (0.01
mol) in 5 ml. of absolute ethanol. The yield of deep blue
hygroscopic crystals is 2.7 g . (42%). Anal. Calcd. for
[NEt4]2[NiBr4]: C, 30.0; H, 6.3; N, 4.4; Br, 50.0; Ni, 9.2.
Found: C, 30.4; H, 6.5; N, 4.6; Br, 49.8; Ni, 9.0. It is not
possible to prepare pure samples of the tetraiodo compound
TETRAHALO COMPLEXES OF DIPOSITIVE METALS 141
because of the difficulty of separation from the starting
materials, which tend to crystallize simultaneously with the
product .
E. COPPER COMPOUNDS
These are prepared in the way described for the manga-
nese compounds and are recrystallized from absolute
ethanol.
1. Bis(tetraethy1ammonium) tetrachlorocuprate (11).
Amounts of reagents used are 0.85 g . CuC12-2H20 (0.005
mol) in 5 ml. of absolute ethanol and 1.84 g. NEt4ClmH20
(0.01 mol) in 5 ml. of absolute ethanol. The yield of yellow
crystals is 2.1 g. (94%). Anal. Calcd. for [NEt4I2[CuC14]:
C, 41.3; H, 8.7; N, 6.0; C1, 30.4. Found: C, 41.1; H, 8.9;
N, 5.9; C1, 29.4.
2. Bis(tetraethy1ammonium) tetrabromocuprate(I1).
Amounts of reagents used are 1.48 g. CuBr2.4Hz0 (0.005
mol) in 10 ml. of absolute ethanol and 2.11 g. NEt4Br (0.01
mol) in 5 ml. of absolute ethanol. The yield of purple
crystals is 2.5 g. (80%). Anal. Calcd. for [NEt4I2[CuBr4]:
C, 29.9; H, 6.3; N, 4.4; Br, 49.6. Found: C, 29.9; H, 6.3;
N, 4.0; Br, 49.5.
Properties
The x-ray powder patterns of the chloro compounds
(except CuC14") are very similar. As the [CoC14I2- ion
is tetrahedral,2 all the chloro complexes must have this
structure, although slight deformations are not ruled out.
Similarly, the crystal properties of the bromo and iodo com-
plexes show that these are tetrahedral.3.4 The tetrachloro-
cuprate(I1) ion has been shown to be a distorted tetra-
h e d r ~ n . ~ The magnetic and spectral properties of these
complexes and the related isocyanato complexes6 have been
reported. 3, 7-10
References
1. K. H. GAYER AND L. WOONTNER: INORGANIC SYNTHESES, 6, 179 (1957)
2. B. MOROSIN and E. C. LINGAFELTER: Acta Cryst., 12, 611 (1959).
142 INORGANIC SYNTHESES
3. N. S. GILL and R. S. NYHOLM: J. Chem. SOC., 1969. 3997.
4. N. S. GILL: ibid., 1961, 3512.
5. B. MOROSIN and E. C. LINOAFELTER: J. Phys. Chem., 66, 50 (1961).
6. D. FORSTER and D. M. L. GOODGAME: J. Chem. SOC., 1964, 2790.
7. F. A. COTTON, D. M. L. GOODGAME, and M. GOODGAME: J Am. Chem.
8. R. J. H. CLARK and T. M. DUNN: J Chem. Soc., 1963, 1198.
9. A. SABATINI and L. SACCONI: J. Am. Chem. SOC., 86, 17 (1964).
SOC., 83, 4161 (1961).
10. D. M. ADAMS, J. CHATT, J. M. DAVIDSON, and J. GERRAT: J. Chem.
Soc., 1963, 2189
37. TRIORTHOPERIODATOTETRACOBALTIC (111)
ACID
4Na3[Co(C03)3]-3Hz0 + 15HC104 + 3NaIo4 .+
H3[Co413024H12].~H20 + 12C02 + (3 - s ) H20 + 15NaC104
SUBMITTED BY JACK M. WILLIAMS* AND C. J. NYMAN*
CHECKED BY ADRIENNE E. WICKENDENt AND RONALD A. KRAUSEt
Hypochlorite oxidation of cobalt(I1) to cobalt(II1) in
basic periodate solution yields the solid complex Na5[Co-
(H2106)2(OH)2].8Hz0. Subsequent dissolution and acidifi-
cation of this salt produces the dark green crystalline acid
H~ [ COJ ~ O~ ~ H~ ~ ] - XH~ O upon standing 12 to 24 hours.
Malaprade2 has prepared the material by a somewhat simi-
lar process. The following procedure is much more conven-
ient than the foregoing because it gives a better yield and
it eliminates the difficult preparation of Na5[Co(H2106) 2-
(OH) 2].8H20.
Procedure
Four and nine-tenths grams (0.025 mol) of sodium meta-
Nine and eight- periodate is dissolved in 75 ml. of water.
* Washington State University, Pullman, Wash.
t The University of Connecticut, Storrs, Conn.