Inorganic Syntheses, Volume VI

Edited by Eugene G. Rochow

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

172 INORGANIC SYNTHESES

2. anorg. Chem., 42, 445 (1904).

2. J . MILBAUER:
3. H. GRWITSCH:“Anorganisch-praparativen Chemie,” p. 391, Springer-
Verlag, Berlin, 1950.
4. A. F. WELLS:“Structural Inorganic Chemistry,” p. 406, Oxford Univer-
sity Press, New York, 1950.
5. K. PREIS:J . prakt. Chem., 107, 12 (1869).
6. G. FOEX:“Tables de constantes et donnhes numeriques no. 7,constants
selectionnhes diamagnetismes et paramagnetisme relaxation para-
magnetique,” p. 73, Gorter and Smits, Paris, 1957.
7. K. PREIS:J. prukt. Chem., 107, 4 (1869).
8. GMELIN:“Handbuch der anorganischen Chemie,” System No. 59,
Fe(B), p. 924, Verlag Chemie, Berlin, 1932.
9. R. SCHNEIDER: Pogg. Ann., 136, 462 (1869).
10. J . MILBRAUER: 2. unorg. Chem., 42, 447 (1904).

64. IRON(I1) CHLORIDE

CCHsCl + 2FeC13-+ C6H4C12 + 2FeC12 + HC1

AND NEAL 0. BRACEt
SUBMITTED BY PETER KOVACIC*
CHECKEDBY T. M. STANLEY,# DAVIDWILLLAMS,~AND A. L. ALLREDS

Anhydrous iron(I1) chloride has been prepared by passing

hydrogen chloride over iron, by reducing iron(II1) chloride
with hydrogen, and by dehydrating one of the hydrates of
iron(I1) chloride. A new procedure is outlined here.lt2

Procedure
Two hundred and twenty-five grams (2 mols) of chloro-
benzene and 162 g. (1 mol) of C.P. anhydrous iron(II1)
chloride are added to a three-necked, round-bottomed flask
equipped with a thermometer, efficient paddle stirrer, and
condenser. Arrangements are made to pass the hydrogen
chloride which is evolved during the reaction through a
* Case Institute of Technology, Cleveland, Ohio.
t E. I. du Pont de Nemours & Company, Wilmington, Del.
2 Northwestern Univenity, Evanston, Ill.
 CARBONATOTETRAMMINECOBALT(III) NITRATE 173

safety trap and into a beaker of water where the acid is

titrated with 2 N sodium hydroxide solution.
The mixture is stirred at a rapid rate and heated for 30
minutes to 126", whereupon the black slurry thickens.
Only approximately 1 ml. of the sodium hydroxide is con-
sumed in this initial heating. The reaction is then allowed
to proceed rapidly at 128 to 139"for 2 hours. In the course
of the reaction the mixture becomes light tan and appreci-
ably less viscous, and the theoretical amount of sodium
hydroxide is required to neutralize the hydrogen chloride
which is evolved. Very little additional hydrogen chloride
is liberated during another hour of heating.
The solid is filtered, washed repeatedly with chloroform
or benzene, and dried in vacuo; the yield is 99%. Anal.
Calcd. for FeClz: Fe, 44.06. Found: Fe, 43.89.

References
and N. 0. BRACE:
1. P. KOVACIC J . Am. Chem. SOC.,76,5491 (1954).
2. N. 0. BRACE:
U.S. patent 2,719,074 (1955).

66. CARBONATOTETRAMMINECOBALT(111)
NITRATE

SWMITTEDBY G. SCHLESSIXCER*
CHECKEDBY JOHN W. SIMNONS,~ J A B S , ~ A N D MARK M.
GERHARDT
CH~~MBERLAIN~

The first salts of this series were prepared by Vortmann'

and later extensively investigated by J$rgensen,2, who, how-
ever, gave only semiquantitative synthetic preparations.
* University of Pennsylvania, Philadelphia, Pa.
t Western Reserve University, Cleveland, Ohio.