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74 Organometallic Compounds

mixture of dichloromethane-hexane. (The yields are ca. 67, 7 5 , and 7556,


respectively .)

References
1. G. B. Deacon, J. H. S. Green, and R. S. Nyholm, J. Chem. SOC.,3411 (1965).
2. G. B. Deacon and J. C. Parrott, J. Organometal. Chem., 17, P17 (1969).
3. R. S. Nyholm and P. Royo, J. Chem. SOC.Chem. Comm., 42 1 (1969).
4. R. U d n , P. Royo, and A. Laguna, J. Organometal. Chem., 69,361 (1974).
5. R. U d n , P. Royo, J. Fornigs, and F. Martinez, J. Organometal. Chem., 90, 367 (1975).
6. F. Caballero and P. Royo, Synth. React. Inorg. Metalorg. Chem., 7 , 351 (1976).
7. P. L. Coe, R. Stephens, and 1. C. Tatlow, J. Chem. SOC.,A , 3227 (1962).
8. E. H. Amonoo-Neizer, R. A. Shaw, D. 0. Skovlin, and B. C. Smith, Inorg. Synth., 8,
19 (1966).
9. R. U d n , A. Laguna, and T. Cuenca, J. Organometal. Chem., 194,271 (1980).

16. (v6-HEXMETHY LBENZENE)RUTHENIUM COMPLEXES

Submitted by M. A. BENNElT,* T.-N. HUANG,* T. W. MATHESON,* and A. K. SMITH?


Checked by STEVEN Il'TELS and WILLIAM NICKERSONS

Areneruthenium(I1) complexes, [Ru($-arene)Cl,] have interesting catalytic


properties4-' and are useful synthetic precursors to a range of arene complexes
of zerovalent and divalent r ~ t h e n i u m . ' ~ Most
~ ' ~ - of
~ the complexes can be made
by reaction of ethanolic ruthenium trichloride with the appropriate 1,3- or 1,4-
cy~lohexadiene.'-~ However, the hexamethylbenzene complex, { RuClz [$-
C6(CH3),}] 2 , one of the more soluble and stable members of the series, cannot
be prepared in this way because hexamethylbenzene cannot be reduced easily to
the corresponding 1,4-diene by dissolving metal reduction. It is necessary first to
prepare the 1-isopropyl4-methylbenzene @cymene) complex, { RuC12[$-1-
[CH(CH&] 4-CH3C6H4}] 2 , by reaction of ruthenium trichloride with commer-
cially available a-phellandrene (5-isopropyl-2-methyl-l,3-cyclohexadiene), and
the coordinated p-cymene can then be displaced quantitatively with hexamethyl-
benzene.

*Research School of Chemistry, The Australian National University, Canberra, A.C.T.,


Australia 2600.
t Department of Inorganic Chemistry, University of Liverpool, Liverpool, England L69 3BX.
$Central Research and Development Dept., Experimental Station, E. I. du Pont de Nemours
and Co., Wilmington, DE 19898.
16. (q6-Hexarnethylbenzene)rutheniurnComplexes 15

A. DI-p-CHLORO-BIS[CHLOR0(~6-1-ISOPROPYL-4-METHYL-
BENZENE)RUTHENIUM(II)]

Procedure
A solution of hydrated ruthenium trichloride (approximating RuC13.3H20,
containing 38-39% Ru, available from Johnson-Matthey Co. Ltd., 78 Hatton
Garden, London, England EClN 8EE) (2 g, approx. 7.7 m o l e ) in 100 mL
ethanol is treated with 10 mL a-phellandrene (Fluka AG, CH-9470, Buchs SG,
Switzerland) and heated under reflux in a 150-mL, round-bottomed flask for 4
hours. A nitrogen atmosphere can be used but is not strictly necessary. The
solution is allowed to cool to room temperature, and the red-brown, micro-
crystalline product is filtered off. Additional product is obtained by evaporating
the orange-yellow fitrate under reduced pressure to approximately half-volume
and refrigerating overnight. After drying in vacuo (approximately 10- torr),
the yield is 1.8-2.0 g (78-87%).
Anal, Calcd. for C20H2sC14Ru2:C, 39.2; H, 4.6; C1, 23.2; MW 612. Found:
C,39.4;H,4.5;Cl,23.3;MW (osmometry inCHC13)604.

Propert ies
The compound is soluble in chloroform and dichloromethane and sparingly
soluble in methanol, acetone, and tetrahydrofuran. It is almost insoluble in
aromatic and petroleum solvents. Solutions and solid are air stable. The com-
pound melts at 200'. (The checker reports 209-230", depending on rate of
heating.) The 100-MHz 'H nmr spectrum in CDC13 (TMS internal standard)
shows resonances at 6 1.26 (doublet, CHCH3, J = 7 Hz), 2.13 (singlet, CH3),
2.88 (septet, CHCH3), and 4.604.72 (doublet of doublets, C6H4, J = 6 Hz).
The far-IR spectrum (Nujol) shows medium-strong bands at 292, 260, and
250(sh) cm-' due to Ru-C1 stretching vibrations.

B. DI-P-CHLORO-BIS[CHLORO($-HEXAMETHYL-
BENZENE)RUTHENIUM(II)]
76 Organornetallic Compounds

Procedure
, ) .O
A mixture of the p-cymene complex [ R U C ~ , ( Q ~ - C ~ ~ H ,(1 ] g, 1.63 mmole)
and hexamethylbenzene (10 g, excess) is heated to 180-185" with magnetic
stirring for 2 hours. The reaction may be carried out in an open or stoppered
flask in an oil bath (an inert atmosphere is not necessary). The crystals of
hexamethylbenzene which sublime to the upper walls of the flask are periodi-
cally scraped down into the melt. The melt is allowed to come to room tempera-
ture, and the solid is broken up and transferred to a pad of Filter Aid. pCymene
and some of the excess of hexamethylbenzene are removed by washing with
diethyl ether or hexane ; the residual hexamethylbenzene is best removed by
sublimation (40°/10-' torr). The solid is washed through the Filter Aid with
chloroform or dichloromethane until the washings are colorless (approximately
200 mL is required). The compound is crystallized by addition of hexane and
evaporation of the orange-red solution. The yield is 0.87 g (80%).
Anal. Calcd. for C24H36C14R~Z: C, 43.1; H, 5.4;C1,21.2;MW 669. Found: c ,
43.3;H, 5.5;Cl, 21.9;MW (osmometry) 690.

Properties
The reddish-brown solid is similar in appearance and solubility to the p-cymene
complex and is air stable as a solid and in solution. It melts at 270". The 100
MHz 'H nmr spectrum in CDC13 (TMS internal standard) shows a singlet due to
the methyl protons at 6 2.03. The IR spectrum shows strong bands at 299
and 258 cm-' (broad) due to Ru-Cl stretching vibrations.

c. BIS(Q~-ETHYLENE)(Q~-HEXAMETHYLBENZENE)RUTHENIUM(O)

All manipulations must be carried out in an inert atmosphere using degassed


~ a 25-mL, round-bottom flask fitted with a nitrogen inlet, reflux
~ o l v e n t s .To
condenser, and magnetic stirring bar is added the di-chloro(@-hexamethyl-
benzene)ruthenium dimer (0.2 g, 0.3 mmole). Under a counterstream of
ethylene, anhydrous sodium carbonate (0.2 g) and ethanol (15 mL) are added.
The mixture is stirred and heated under reflux under a slow flow of ethylene for
2 hours; the solution initially turns deep red and finally becomes brown. After
cooling to room temperature, solvent is stripped in vacuo and the residue is
extracted with four 5 mL portions of hexane. The filtered extract is concen-
16. (r,6-Hexarnethylbenzene)rtheniumComplexes I1

trated under reduced pressure to about 5 mL and cooled to - 78". The off-white
needles are washed by decantation with two 2-mL portions of cold isopentane
(2-methylbutane) and are dried in vacuo. The yield is 0.07 g (37%).
Anal. Calcd. for C 1 6 H 2 6 R ~c :, 60.2; H, 8.2; MW 320. Found: c , 60.2; H, 8.1;
MW (mass spectrometry) 320 ("'Ru).

Properties
The compound is an air-sensitive solid which should be stored under an inert
atmosphere in a refrigerator. It dissolves in all common organic solvents giving
very air-sensitive solutions. The 100-MHz 'H nmr spectrum in C&6 (internal
TMS) exhibits two multiplets at S 1.04 and 1.48 due to the protons of coordi-
nated ethylene and a singlet at 6 1.70 due to the methyl protons of hexamethyl-
benzene. The IR spectrum (Csl disk) shows a weak band at 1480 cm-* which
may be due to a mixed C=C stretching/CH2 deformation mode of coordinated
ethylene.

D. ( ~ ~,~-CYCLOHEXADIENE)(Q~-HEXAMETHYL-
- 1
BENZENE)RUTHENIUM( 0)

All manipulations must be carried out in an inert atmosphere using degassed


solvents. To a 25-mL, round-bottom flask fitted with a nitrogen inlet, reflux
condenser, and magnetic stirring bar is added the di-chloro($-hexamethylben-
2ene)ruthenium dimer (0.2 g, 0.3 mmole), anhydrous sodium carbonate (0.2 g),
1,3-~yclohexadiene(Chemsampco, 4692 Kenny Road, Columbus, OH 43320,
formerly Chemical Samples Co.; or Ega Chemie, 7924 SteinheimlAlbuch, W.
Germany) (1 mL, 0.8 g, 1.O mmole) and ethanol or 2-propanol(l5 mL). Slightly
lower yields are obtained if 1,4-~yclohexadiene,prepared by Birch reduction of
benzene, is used instead of 1,3-~yclohexadiene.The mixture is stirred and heated
under reflux for 2.5 hours, during which time the suspended dimer dissolves and
the solution turns yellow. Volatile liquids are removed in vacuo, and the residue
is extracted with four 5-mL portions of hexane. The filtered extract is concen-
trated in vacuo and cooled to -78". The pale-yellow crystals are washed by
decantation with two 2-mL portions of cold isopentane (2-methylbutane) and
dried in vacuo. The yield is 0.13 g (63%).
Anal. Calcd. for C18H26R~: C, 62.8; H, 7.6; MW 344. Found: C, 63.2;H, 7.2;
MW (mass spectrometry) 344 ("'Ru).
78 Organometallic Compounds

Properties
These are similar to those of the corresponding bis(ethy1ene) complex. The 100-
MHz 'H nmr spectrum in C6Db (internal TMS) shows a pair of multiplets at
6 2.41 and 4.41 due to the outer and inner coordinated diene protons, respec-
tively, a multiplet at 6 1.71 due to the methylene protons, and a singlet at
6 1.95 due to the methyl protons of hexamethylbenzene.

References
1. G. Winkhausand H.Singer,J. Organometal. Chem., 7 , 4 8 7 (1967).
2. R. A. Zelonka and M. C. Baud, Can. J. Chem., 5 0 , 3 0 6 3 (1972).
3. M. A. Bennett and A. K. Smith, J. Chem. SOC.,Dalton Trans., 233 (1974).
4. I. Ogata, R. Iwata and Y . Ikeda, Tetrahedron Lett., 3011 (1970). R. Iwata and I. Ogata,
Tetrahedron, 2 9 , 2 7 5 3 (1973).
5. A. G. Hinze, R e d . Trav. Chim. Pays-Bas, 9 2 , 5 4 2 (1973).
6. M. A. Bennett, T-N. Huang, A. K. Smith and T. W. Turney, J. Chem. SOC. Chem.
Comm., 582 (1978).
7. M. A. Bennett, T-N. Huang and T. W. Turney, J. Chem. SOC.Chem. Comm., 312 (1979).
8. For example: R. A. Zelonka and M. C. Baud, J. Organometal. Chem., 44, 383 (1972).
R. H. Crabtree and A. J. Pearman, ibid., 141, 325 (1977). D. R. Robertson, T. A.
Stephenson and T. Arthur, ibid., 162, 121 (1978). M. A. Bennett,T. W. Matheson, G. B.
Robertson, W. L. Steffen and T. W. Turney, J. Chem. SOC.Chem. Comm., 32 (1979).
M. A. Bennett and T. W. Matheson, J. Organometal. Chem., 153, C25 (1978). Idem.,
ibid., 175, 87 (1979). H. Werner and R. Werner, Angew. Chem. Int. Ed. Engl., 17,683
(1978).Idem.,J. Organometal. Chem., 174,C63,C67 (1979).
9. D. F . Shriver, The Manipulation of Air-Sensitive Compounds, McCraw-Hill, New York,
1969, Chap. 7.

17. SOME 77'-CYCLOPENTADIENYLRUTHENIUM(I1)


COMPLEXES CONTAINING TRIPHENYLPHOSPHINE

Submitted by M. 1. BRUCE,* C. HAhfEISTER,* A. G. SWINGER,* and R C. WALLIS*


Checked by S. D. ITTEL?

The chemistry of R u C I ( P P ~ ~ ) ~ ( $ - C ~differs


H ~ ) markedly from that of the
corresponding dicarbonyl complex, R U C ~ ( C O ) ~ ( $ C ~ H ~The
) . ' triphenylphos-
phine complex was first described by Gilbert and Wilkinson: who obtained it

*Department of Physical and Inorganic Chemistry, University of Adelaide, Adelaide, South


Australia 5001.
tCentral Research and Development Department, E.I. du Pont de Nemours and Co.,
Wilmington, DE 19898.

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