Inorganic Syntheses, VolumeI1

Edited by W Conard Fernelius

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

196 I NO RGA N I C SYNTHESES

solid is not wetted by water. Hydration is catalyzed by

substances that either react with the anhydrous compound
or alter the surface tension at the salt-water intelface.
The solid slowly dissolves on the addition of chromium(I1)
chloride. The anhydrous chloride reacts with anhydrous
ammonia, forming chloropentamminechromium(II1) chlor-
ide together with some hexamminechromium(II1) chloride.
References
1. MELLOR: “A Comprehensive Treatise on Inorganic and Theoretical
Chemistry,” Vol. 11, p. 371, Longmans, Green and Company, New
York, 1931.
2. HENDERSON and FERNELIUS: “A Course in Inorganic Preparations,”
p. 68, McGraw-Hill Book Company, Inc., New York, 1935.
3. UFER:Ann., 228, 112 (1885).
4. HALL:J. Am. Chem. Soc., 26, 1244 (1904).
5. DEMAACAY: Compt. rend., 104, 112 (1887).
6. COMBAULIVES: ibid., 150, 175 (1910).

60. TRIS(ETHYLENEDIAMINE)CHROMIUM(III)
SALTS
cr2(so4)3 + 6C2H4(NH2), + [Cr(en)3I2(SO4)3
CARL L. ROLLINSON*t AND JOHN
S U B M I T T E D BY c. BA~LAR, JR.*
CHECEED
B Y LAURENCE S. FOSTER$$AND GABRIELG E V E R ~
The chromium(II1) ammines closely resemble the cor-
responding cobalt(II1) complexes in many respects. For
example, analogous compounds in the two series are usually
isomorphous and of similar color. While the preparative
methods used for cobalt(II1) ammines can sometimes be
employed for the preparation of the corresponding chro-
mium(II1) ammines, other methods are usually preferred.
Thus a mixture of a chromium(I1) salt and ethylenedia-
mine .absorbs atmospheric oxygen even more readily tha.n
does a mixture of a cobalt(I1) salt and the base. The pro-
cedure for preparing tris(ethylenediamine)chromium(III)
* University of Illinois, Urbana, 111.
t Present address: Central Research Department, Monsanto Chemical
Company, Dayton, Ohio.
3 Brown University, Providence, R.I.
8 Present address: Watertown Arsenal, Watertown, Mass.
 TRIS(ETHYLENEDIAMIKEjCHROiMIUlM(IIIjSALTS 197

salts1 based on this reaction is rather tedious. Conse-

quently, methods beginning with readily available chro-
mium(II1) salts are commonly employed.
Molecules that coordinate strongly can often displace
others from the coordination sphere. Ethylenediamine
does not readily replace water from the hydrated chro-
mium(II1) ion, but it does readily displace pyridine.
Pfeiffer has described the preparation of tris(ethy1enedia-
mine)chromium(III) chloride from trichlorotripyridine-
chromium2 and the corresponding sulfate from dehydrated
chrome alum.
The method outlined here4 is similar to the latter
but obviates the separation of potassium sulfate from
the product. The new methods described below for
obtaining various tris(ethylenediamine)chromium(III) salts
with anhydrous chromium(II1) sulfate as the starting
material can be used also for preparing the corresponding
propylenediamine derivative^.^
Procedure
A. ANHYDROUS CHROMIUM(II1) SULFATE
Hydrated chromium(II1) sulfate is dehydrated by heat-
ing for several days in an oven at 100 to 110". The mate-
rial, originally lumpy, can be ground to a powder after the
first 2 or 3 days and then returned to the oven for further
drying. Dehydration is complete when the powder fails
to dissolve in water.
B. ANHYDROUS ETHnENEDIAMINE
Aqueous ethylenediamine is dehydrated by a modifica-
tion of the method of Putnam and Kobe.5 Five hundred
grams of solid sodium hydroxide and 875 ml. of commercial
(70 per cent) ethylenediamine are digested on the steam
bath overnight.* The hot Liquid separates into two layers,
* It is necessary to cover all corks with tin foil or aluminum foil in this
procedure, as ethylenediamine vapor attacks cork readily. Ethylene-
diamine also attacks rubber.
198 INORGANIC SYNTHESES

the upper of which is decanted, digested with a new portion

of sodium hydroxide (150 g.) for several hours, decanted
again, and distilled. The boiling point is 116 to 117" at
760 mm. Yield almost quantitative." This method may
also be used to dehydrate propylenediamine.
C. TRlS(ETHYLENEDIAMINE)CHROMIUM(III)SULFATE,
"%en) &(SO&
Forty-nine grams (0.125 mol) of anhydrous chro-
mium(II1) sulfate and 50 ml. (0.75 mol) of dehydrated
ethylenediamine are heated on the steam bath in a 300-ml.
Erlenmeyer flask fitted with an air condenser; the stopper
is covered with tin foil. Within an hour (often much less),
the sulfate begins to lose its bright-green color and pow-
dery character. If this does not happen within a few hours,
a drop of water may be added to accelerate the reaction.
From this point on, the flask must be shaken at intervals
to keep the unchanged sulfate exposed to the amine.
Finally, a brown mass is formed, and no excess liquid is
present. The flask is left on the steam bath overnight.
The orange-yellow mass is broken up with a spatula and
ground to a powder, which is washed with alcohol and
allowed to dry in air. Yield 89 g. [95 per cent based on
CrdSO~>~l.
D. TRIS(ETHYLENEDIAMINE)CHROMIUM(III)CHLORIDE,
HYDRATE, [Cr(en)a]C13.3xH20
Thirty-two grams (0.043 mol) of the tris(ethy1enedia-
mine) sulfate is dissolved in a mixture of 30 ml. of water
and 5 ml. of concentrated hydrochloric acid at 60 to 65".
The hydrochloric acid is necessary to prevent the forma-
tion of a red product, evidently formed by reaction of the
* If the ethylenediamine is too dry, it reacts very slowly with the anhy-
drous chromium(II1) salt. The full procedure described by Putnam and
Kobe should not, therefore, be used in this synthesis. Their procedure
involves refluxing the material decanted from the sodium hydroxide with
40 g. of metallic sodium before distilling. The yield is cut to about 75 per
cent by this process.
 T R I S ( E T H Y L E N E D 1 A M I N ECHROMI
) U M ( I I I ) SALTS 199

sulfate with warm water, which not only decreases the

yield but makes filtration very slow. The solution is
filtered rapidly in a Buchner funnel. Twenty-seven mil-
liliters of concentrated hydrochloric acid mixed with 42
ml. of alcohol is added to the filtrate, which is cooled in ice
and stirred. The chloride separates in yellow crystals.
Yield 20 g. of crude material (60 per cent based on the
sulfate).
The product prepared in this way is contaminated with
sulfate and may be purified by recrystallization from water.
A solution of 20 g. of the crude product dissolved in 20 ml.
of water at 65" yields on cooling, 12 g. of pure product (60
per cent based on crude chloride or 36 per cent based on the
sulfate).
E. TRIS(ETHYLENEDIAMINE)CHROMIUM(III)HALIDES,
[Cr(en)a]X3 (X = Br, I, or SCN)
The bromide, iodide, and thiocyanate can be prepared
from the chloride by adding a 100 per cent excess of the
solid sodium or ammonium salt of the desired anion to
30 g. of the tris(ethy1enediamine) chloride in 100 ml. of
warm water. The solution is stirred rapidly and cooled in
ice. I n each case, crystallization starts as soon as the salt
is added. The salt is filtered by suction. The crude salt
is recrystallized from water at 65". After the solution
has cooled, the crystals are filtered by suction, washed
with alcohol and ether, and air-dried. Typical experi-
mental yields are given in the following table:

NHIX or NaX Grams of

Grams of pure
Desired salt required for crude product
HzO for product and
[Cr(en)3]Xs 0.075 mol and percentage
recrystal- percentage
yHzO where chloride, 100
yield based on lization, ml. yield based
X and y are per cent [Cr(en)3]Clr
on crude salt
excess, g. 3% HzO

1 1 1 ;i: 1
I I I I
Br- 4H20 44-46 40 g., 98% 75 31 g., 78%
I- H20 65-68 45 g., 96% 32 g., 71 %
SCN- H20 34-36 30 g., 94% 23 g., 77%
200 INORGANIC SYNTHESES

Properties
The tris(ethylenediamine)chromium(III) salts (luteo
chromic salts) are all markedly crystalline, orange-yellow
substances. While the sulfate is extremely soluble and
the chloride highly soluble in water, the bromide, iodide,
and thiocyanate are relatively insoluble. All of these salts
are slowly decomposed in cold water and rapidly in hot
water, forming deep-red gummy materials, which are evi-
dently hydroxoamminechromium compounds. The dry
salts are slowly decomposed by exposure to light. The dry
chloride and thiocyanate are decomposed readily by heat
to bis(ethy1enediamine) salts (synthesis 61).
References
1. and BAILAR:J . Am. Chem. SOC.,68, 1474 (1936).
BALTRIS
2. 2. anorg. Chem., 24, 286 (1900).
PFEIFFER:
3. Ber., 37, 4277 (1904).
PFEIFFER:
4. ROLLINSONand BAILAR:J . Am. Chem. Xoc., 65, 250 (1943).
5. PUTNAMand KOBE:Trans. Am. Electrochem. Xoc., 74, 609 (1934).

61. CIS-DICHLOROBIS (ETHYLENEDIAMINE) -

CHROMIUM(1II) CHLORIDE AND TRANS-BIS-
(THIOCYANAT0)BIS (ETHYLENEDIAM1NE)-
CHROMIUM (III) THIOCYANATE
+ (XJ =
[ ~ r ( e n ) i j ~ ~ h " ' t t e[nC ~ ( ~ ~ ) * X X CI or SCN)
BY CARLL. ROLL INS ON*^ AND JOHN
SWMITTED C. BAILAR,JR.*
P. MCREYNOLDSS
BY JAMES
CHECKED

The tris(ethylenediamine)chromium(III) salts are much

less stable than their cobalt analogs, and lose one molecule
of ethylenediamine readily. The temperature of decompo-
sition depends upon the nature of the anion, part of which
ent,ers the complex cation during the thermal decomposi-
tion. The reaction has been studied in detail for the
* University of Illinois, Urbana, Ill.
iPresent address: Central Research Department, Monsanto Chemical
Company, Dayton, Ohio.
$ The Ohio State University, Columbus, Ohio; deceased.