Inorganic Syntheses, VolumeI1

Edited by W Conard Fernelius

Copyright © 1946 by McGraw-Hill Book Company, Inc.

TRIS(ETHYLENEDIA,VLINE)COBALT(NI)CHLORIDE 22 1
5. J . prakt.
JORGENSEN: Chem., [2] 23, 229 (1881).
6. RIILLs: Phil. Mag.; [4] 36, 245 (1868).
7. B ~ u N Ann.,
: 142, 52 (1867).
8. JACOBSEN: Overs. Danske Sclsk. Forh., 1899, 564.
9. Ref. 2, p. 457.
10. BILTZ:Z. anorg. Chem., 83, 178, (1914).
11. BILTZand BILTZ:(trans. by Hall and Blanchaid): “Laboratory Methods
of Inorganic Chemistry,” p. 175, John Wiley & Sons, Inc., New York,
1909.
12. Ref. 8, p. 575.
13. Ref. 10, p. 177.
14. BJERRUM:“Metal Ammine Formation in Aqueous Solution,” p. 241,
P. Haase and Son, Copenhagen, 1041.
15. SORENSEN:dissertation, p. 64, Copenhagen.
16. GMELIN: “Handbuch der anorganischen Chemic,” No. 58 B (Kobalt-
ammine), pp. 46-72, Verlag Chemie G.m.b.H., Eerlin, 1930.

70. TRIS (ETHYLENEDIAMINE) COBALT(II1)

CHLORIDE
4C0C12 + 8CzH4(NHz)z + 4C2Hj(n’Hz)z*HC1+
+ 2Hz0
0 2 4
4[Co(en),]C13
J. B. FIrORK*
SWXITTED B Y
BY JAMES
CHECKED P. MCREYNOLDS~
Ethylenediarnine coordinates with metallic ions through
both nitrogen atoms. The five-membered chelate rings
that are thus formed are very stable. Many cobalt(II1)
ammines are converted by aqeuous ethylenediamine to
tris(ethylenediamine)cobalt(III) chloride. Thus, Jorgen-
sen1 prepared the salt by heating [Co(NH3),C1]C12with
aqueous ethylenediamine. Grossmaii and Schuck2obtained
the salt by oxidizing a mixture of cobalt(I1) chloride,
ethylenediamine, and water. The method described below
has been developed from the latter suggestion.

Procedure
Sixty-one grams of 30 per cent ethylenediamine is partly
neutralized with 17 ml. of 6 N hydrochloric acid and the
* UrGversity of Illinois, Urbana, Ill.
t The Ohio State University, Columbus, Ohio: deceased,
222 INORGANIC SYMTHESES

resulting mixture poured into a solution of 24 g. of cobalt

chloride 6-hydrate in 75 ml. of water. The cobalt is
oxidized by bubbling a vigorous stream of air through the
solution for 3 hours. The solution is allowed to evaporate
on a steam bath until a crust begins t o form over the sur-
face (the-volume will be about 15 to 20 ml.); then 15 ml.
of concentrated hgdrochloric acid and.30 ml. of ethyl alco-
hol are added. After cooling, the crystals of tris(ethy1ene-
diamine)cobalt(III) chloride are filtered and washed with
alcohol until the washings are colorless. They are then
washed with ether or dried in an oven. Yield 31 g. (89
per cent).
Properties
Tris (ethy1enediamine)cobalt(111) chloride crystallizes in
orange-yellow .needles, which are readily soluble in water
but insoluble,in the usual organic solvents. Its solubility
in 6 N hydrochloric acid is about 3 per cent. It is stable
at temperatures as high as 200" and is decomposed only
slowly by hydrogen sulfide and sodium hydroxide.
References
J . pru&t. Chem., [2] 39, 8 (1889).
1. JORGENSEN:
and S C E ~ ~ C
2. GROSSMAN K : 39, 1899 (1906).
Ber.,

71. CIS- AND TRANS-DICHLOROBIS-

(ETHYLENEDIAMINE) COBALT(III) CHLORIDE
AND THE RESOLUTION OF THE CIS FORM
BY J O ~ C.
SUBMITTED Y BAILAR,JR.*
CEECKED
BY CARL L. ROLLLNSON~
Among the inorganic complex compounds that can be
resolved into optically active forms, cis-dichlorobis(ethy1-
enediaLye)cobalt(III) chloride is one of the best known
and easiest to prepare. It is often used in stereochemical
* University of Illinois, Urbana, Ill.
t Grasselli Chemicals Departm?mt, E. I. duPont de Nemours & Company,
Inc., Cleveland, Ohio; present address: Central Research Department,
Monsanto Chemical Company, Dayton, Ohio.