Inorganic Syntheses, VolumeXV

Edited by George W. Paxshall

Copyright © 1974 by McGraw-Hill, Inc.

18 Inorganic Syntheses

cm.
-
'.
It is quite volatile, forming a red crystalline sublimate. Al-
though the pure compound is stable in dry air, its solutions in organic
solvents decompose to insoluble brown materials when left exposed
to air.

References
I. R. Cramer. Inorx. Chcm.. 1.722 (1962).
2. R. Cramer. J . Am. Chern. Soc., 86, 217 (1964).
3. J. A . McCleverty and G. Wilkinson. Inorganic Syntheses, 8, 21 1 (1966).
4. C. W . Gariandand J . R. Wi1t.J. Cham. fhys..36, 1094(1962): A . C. Yangand
C. W. Garland, J . PIzjs. Clzenz., 61, 1504 (1957).

5. CYCLOOCTENE AND 1.5-CYCLOOCTADIENE

COMPLEXES OF IRIDTUM(1)
Submitted by J. L. HERDE.* J. C. LAMBERT,* and C. V. SENOFF*
Checked by M. A. CUSHING'F

The dimeric chloro-bridged complexes [IrCl(l,S-C,H,,)], and

[IrCl(C,H have been synthesized by the reduction of an
iridium(1V) salt in the presence of excess cycloolefin in aqueous
ethanol and aqueous 2-propanol, respectively. These dimeric
'g2

complexes are more conveniently synthesized starting with commer-

cially available hydrated iridium trichloride. The complexes are
useful starting materials for the preparation of the complexes
, ~ well as a series of
IrCl[P(C,H,)3]3 and I ~ C ~ [ A S ( C , H , ) , ] ~as
four- and five-coordinate iridium(1) cations containing phosphite,
phosphine, and arsine l i g a n d ~ . ~

A. DI-p-CHLORO-BIS(l,5-CYCLOOCTADIENE)DIlRlDlUM(I)
21rC13 + 2C8H,, + 2CH3CH,0H-
Ir2C12(C8H,2)2 4HCl+ + 2CH3CH0

*Department of Chemistry, University of Guelph, Guelph, Ontario, Canada.

tCentral Research Department, E. I. du Pont de Nemours & Company, Wilmington,
Del. 19898.
 Olejin Complexes 19

Procedure
A 150-mI., three-necked, round-bottomed flask containing a
magnetic stirring bar is charged with 2.0 g. of iridium trichloride
hydrate,* 34 ml. of 95% ethanol, 17 ml. of water, and 6.0 ml. of
1,5-cyclooctadiene.~One neck of the flask is equipped with an inlet
for nitrogen, another neck is equipped with a water-jacketed con-
denser, and the third neck is equipped with a nitrogen-bubbling
tube. A slow stream of nitrogen is passed through the system, and
the solution is stirred and refluxed for 24 hours, during which time
the brick-red product precipitates from the solution. The mixture is
allowed to cool to room temperature and di-p-chloro-bis( 1,5-
cyclooctadiene)diiridium(I) is collected by filtration, washed with
ice-cold methanol to remove the last traces of unreacted 1,5-cyclo-
octadiene, and then dried in uucuo at 25" for 8 hours. Yield is 1.5 g.
(72 %), m.p. > 200" (decomposes). Anal. Calcd. for C, 6H24C121r2 :
C, 28.61; H, 3.60; C1, 10.56; Ir, 57.23. Found: C, 28.68; H, 3.64; C1,
10.51; Ir, 57.17.

Properties
Di-~-chloro-bis(l,5-cyclooctadiene)diiridium(I) is an orange-red,
air-stable solid. It is soluble in chloroform and benzene, somewhat
less soluble in acetone, and insoluble in ether. Other physical prop-
erties of the complex are given in the literature.'

2IrC1, -
B. DI-p-CHLOROTETRAKIS(CYCLOOCTENE)DIIRIDrUM(T)
+ 4C,H,, + 2(CH,),CH(OH)
Ir2C1,(C,Hl4), + 4HC1 + Z(CH,),CO
Procedure
A 150-ml.,three-necked, round-bottomed flask is charged with 2.0
g. of hydrated iridium trichloride, 22 ml. of 2-propanol (isopropyl

*A suitable starting material with the approximate composition IrC1,. 3H,O is available
from Engelhard Industries, 429 Delancy St., Newark, N.J. 07105.
tl,5-Cyclooctadiene obtained from the Columbian Carbon Co., Inc., Princeton, N.J.,
may be used without further purification.
20 Inorganic Syntheses

alcohol), 8 ml. of water, and 4.0 ml. of cyclooctene.* One neck of the
flask is equipped with an inlet for nitrogen, another neck is equipped
with a water-jacketed condenser, and the third neck is equipped with
a nitrogen-bubbling tube. A slow stream of nitrogen is passed
through the system, and the solution is stirred well at room tem-
perature for a few minutes by means of a magnetic stirring bar.
The solution is refluxed at 78" for 3 hours, during which time it
changes from dark red t o orange-yellow and di-p-chlorotetrakis-
(cyclooctene)diiridium(I) precipitates from the solution. The mixture
is allowed t o cool t o room temperature, and di-p-chlorotetrakis-
(cyclooctene)diiridium(I)is collected quickly by filtration and washed
quickly with ice-cold methanol to remove the last traces of unreacted
cyclooctene. (The filtration and washing can be done better in an
inert-atmosphere box if one is available.) After drying in uucuo
at 25" for 4 hours, the yield is 1.5 g. (59%). M.p. 150" (decomposes).
Anal. Calcd. for C32H56C121r2: C, 42.92; H, 6.25; C1, 7.85; Ir, 42.98.
Found: C , 42.80; H, 6.50; C1, 7.88; Ir, 42.86.

Propert ies
Di-p-chlorotetrakis(cyclooctene)diiridium(I)is an air-sensitive yel-
low solid. Upon exposure to air, it readily decomposes to a dark-green
solid which eventually blackens. It is soluble in benzene, chloroform,
and acetone; solutions in these solvents are extremely sensitive to
oxygen. The complex may be stored for a prolonged period of time
in uucuo in a vacuum desiccator. Other physical properties of the
complex are given in the literature.'

References
1. G. Winkhaus and H. Singer. Chcm. Ber.. 99, 3610 (1966).
2. A. van der Ent and A. L. Onderdelinden, Inorganic Syntheses, 14, 92 (1973).
3. M. A. Bennett and D. L. Milner. J . Am. Chrm. SOC.,91,6983 (1969).
4. L. M. Haines and E. Singleton, J . Chem. SOC.,Dalton Trans., 1972, 1891.
5. J. L. Herde and C. V. Senoff. Inorg. Nztcl. Chcm. Lcrters. 7. 1029 (1971).

*Cyclooctene obtained from the Columbian Carbon Co., Inc., Princeton, N.J., may be used
without further purification.