Inorganic Syntheses, Volume VI

Edited by Eugene G. Rochow

Copyright © 1960 by McGraw-Hill Book Company, Inc.

TRINITROTRIAMMINECOBALT(III) 189

60. TRINITROTRIAMMINECOBALT(III)

+
~ C O ( C ~ H , O 6NaNOz
~)~ +
2NH4C2H302 4NH3(aq.) +
+ +
HzOz+ ~CO(NH,),(NOZ)~6NaCzH30~ 2Hz0 +
SUBMITTEDBY G. SCHLESSINGER*
CHECKED BY WILMA FAYEBARKERt AND MARKM. CHAMBERLAIN4

Trinitrotriamminecobalt is by far the most important

starting material in the triamminecobalt series. It was
first prepared by Erdmannl and later by J$rgensen2 by the
air-oxidation of ammoniacal cobalt (11) salt solutions con-
taining sodium nitrite and much ammonium chloride. It
has also been prepared by heating trans-dinitrotetrammine
salts with sodium nitrite3 and from ammonium tetranitro-
diamminecobaltate(II1) and aqueous a m m ~ n i a . ~
The following method, which is an adaptation of that of
D ~ v a l makes
,~ use of the catalytic effect of charcoal in
forming cobalt-nitrogen bonds and avoids the unnecessary
use of ammonium chloride. This procedure is much shorter
than air-oxidation methods and yields a relatively pure
product in acceptable yield.

Procedure
Fifty grams (0.42 mol) of pure cobalt(I1) carbonate is
prepared by slowly adding a saturated solution of an equiv-
alent quantity of the chloride, nitrate, or sulfate to a hot
solution of 60 g. (0.57 mol) of anhydrous sodium carbonate
in 600 ml. of water. Some effervescence takes place. The
mixture is next digested at the boiling point for 15 minutes
with continuous stirring and then suction-filtered, the solids
* University of Pennsylvania, Philadelphia, Pa.
t Western Fieserve University, Cleveland, Ohio.
190 INORGANIC SYNTHESES

washed freely with water, and pressed as dry as possible on

the filter.*
The cobalt(I1) carbonate prepared as above is dissolved
in a hot mixture of 70 ml. of glacial acetic acid and 140 ml.
of water. This solution is then added to a cold solution of
105 g. of sodium nitrite (1.52 mols) in 500 ml. of concen-
trated ammonia contained in a 2-1. Erlenmeyer flask. The
resulting mixture is well cooled in ice and 280 ml. of 3%
HzOzis slowly added with good swirling. The flask is then
allowed to remain 20 minutes longer in the ice bath and
3.5 g. of activated charcoal is added. The mixture is next
heated for 1 hour over a free flame (in the hood, as much
ammonia escapes) and the volume is kept constant by the
addition of water as necessary. The hot liquid is filtered
rapidly by suction to remove the charcoal, and the filtrate
is cooled in an ice-water mixture. The product that sepa-
rates (crystallization is aided by scratching the walls of the
container) is suction filtered, the filtrate reserved for further
workup, and the solids washed with ethanol and ether and
then air-dried.
To the above filtrate is added 3 g. of charcoal, and the
mixture is then evaporated in a beaker over a free flame
with continuous stirring to a volume of 650 to 700 ml. and
filtered by suction while hot. More product is isolated
from the solution as described above. The total yield is
55 g. (53%). The product may be recrystallized from a
volume of water, faintly acidified with acetic acid, equal to
thirty times the weight of the dry material. This gives an
analytically pure sample, but the crude nonelectrolyte as
obtained above is quite satisfactory for further synthetic
use.
Analysis of the nitro group is performed by decomposing
the complex with dilute sodium hydroxide, running the fil-
trate into an excess of cerium(1V) sulfate (which oxidizes the
* If desired, technical cobalt(I1) carbonate (51g . ) may be dissolved in the
minimum amount of 1:1 hydrochloric acid, filtered, and reprecipitated as
above.
 TRINITROTRIAMMINECOBALT(III) 191

nitrite quantitatively to nitrate), adding potassium iodide,

and back-titrating the iodine with thiosulfate. Cobalt is
determined by dissolving the cobalt(II1) oxide obtained in
alkali, decomposing with acidified potassium iodide, and
titrating the liberated iodine with thiosulfate. Anal.
Calcd. for Co(NH3)3(NOZ)3:Co, 23.8; NOz-, 55.6. Found:
CO,23.8; NOz-, 55.3.

Properties
The complex is brownish yellow or mustard-colored, con-
sisting of thin plates and some orthorhombic prisms. The
solubility in water at 16.5" is 0.177 g./100 g. and at 100"
about 1 g./30 g. Aqueous solutions of the material have a
negligibly small conductivity, thus indicating the formula-
tion of the material as a nonelectrolyte. Concentrated
nitric acid produces the highly hygroscopic triaquotriam-
minecobalt(II1) nitrate. Cold dilute hydrochloric acid
replaces one nitro group in the complex, and oxalic acid in
hot aqueous solution two nitro groups. Warm, concen-
trated hydrochloric acid forms dichloroaquotriammineco-
balt(II1) chloride. A complete description of properties is
available.

References
1. 0. L. ERDMANN: J . prukt. Chem., 97, 412 (1866).
2. S. M. JGRGENSEN: 2. anorg. Chem., 17, 475 (1898).
3. N. R. DHAR:Akud. Amsterdam Versl., 28, 552 (1920).
4. S. M. J~RGENSEN: 2. unorg. Chem., 7, 308 (1894).
5. C. DUVAL: Compt. rend., 182, 636 (1926).
6. GMELIN: "Handbuch der anorganischen Chemie," Vol. 58B, p. 304,
Verlag Chemie, Berlin, 1930.