Ruthenium, Osmium, Rhodium, and Iridium Containing Hydride, Carbonyl, or Nitrosyl Ligands

COMPLEXES OF RUTHENIUM, OSMIUM, RHODIUM, AND IRIDIUM CONTAINING HYDRIDE CARBONYL, OR NITROSYL LIGANDS 

Present addresses Department of Chemistry, Aligarh Muslim University, Aligarh, U.P. India (N.A.) International Nickel Limited, Bashley Road, London, N.W. 10, England (J.J.L.). 

A discussion of the basic technique, apparatus, and reagents employed together with details concerning methods of purification and characterization of products is given in the following section. The success of these syntheses is dependent on strict adherence to the procedures described. 

Carbonylchlorohydridotris(triphenylphosphine)ruthenium(II) was originally prepared by prolonged reaction of ruthenium trichloride and triphenylphosphine in basic alcoholic media.4,5 It is more conveniently obtained from the homogeneous reaction of triphenylphosphine, ruthenium trichloride, and aqueous formaldehyde in boiling 2-methoxyethanol.1 

Solutions of 0.26 g. (1.0 mmole) of hydrated ruthenium trichloride in 20 ml. of 2-methoxyethanol and aqueous formaldehyde (20 ml., 40% w/v solution) are added rapidly and successively to a vigorously stirred, boiling solution of 1.58 g. (6 mmoles) of triphenylphosphine in 60 ml. of 2-methoxyethanol. The mixture is heated under reflux for 10 minutes and allowed to cool. The precipitate which forms is separated and washed successively with ethanol, water, ethanol, and rc-hexane and dried in vacuo. Yield 0.89 g. (93% based on RuC13-3H20). Anal. Calcd. for C55H46C10P3Ru C, 69.36 H, 4.87 Cl, 3.72 P, 9.76. Found C, 69.3 H, 4.94 Cl, 3.36 P, 9.72. 

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