HYDROGENATION AND DEGRADATION OF CARBON-DISULFIDE BY ORGANOMETALLIC CLUSTER HYDRIDE COMPLEXES - REACTION OF CARBON-DISULFIDE WITH (MU-H)2OS3(CO)9[P(CH3)2C6H5]

It has recently been proposed that transition metal cluster compounds may form the basis for the development of a valuable new class of homogeneous catalysts. This idea is based on the principle that the cooperative interaction of several metal atoms with a given substrate or substrates can produce new and unusual forms of reactivity.12 We have recently been examining the ability of triosmium-hydride cluster complexes to effect the hydrogenation of small molecules3 and have found that (μ-H)2Os3(CO)10reacts with CS2 via an unusual dicluster reaction to produce the molecule (μ-S2CH2)[(μ-H)-Os3(CO)10]2.3b In this reaction each cluster has transferred one hydrogen atom to the carbon atom of the CS2 molecule and produced a dithiomethylene ligand which then links the two cluster units. In an effort to gain further insight into the mechanism of this unusual reaction we have examined the reaction of (μ-H)2Os3(CO)9[P(CH3)2C6H5] with CS2. To our surprise, we have found an entirely new reaction in which a single cluster complex reacts with one molecule of CS2, transfers both its hydrogen atoms to the carbon atom, cleave a single sulfur atom from the original CS2 unit, and ultimately produces a fractured cluster complex containing inorganic sulfide and a bridging thioformaldehyde ligand. © 1979, American Chemical Society. All rights reserved.