Reactivity of 2-(Diphenylphosphanyl)thiophenol (HSC6H4PPh2) with Ruthenium and Osmium Carbonyl Complexes; Breaking of HSC6H4PPh2 into Sulfide, Phenyl and Diphenylphosphanyl Ligands on a Triruthenium Cluster

2-(Diphenylphosphanyl)thiophenol (HSC6H4PPh2) reacts with the carbonyl clusters [Ru3(CO)12] and [Os3(CO)10(MeCN)2] to give mixtures of products, the composition of which depends upon the reaction conditions and the ratio of the reactants. The derivatives [M3(μ-H)(μ-η2-SC6H4PPh2)(CO)9] (1a: M = Ru; 1b: M = Os), [Ru3(μ3-S)(μ-η2-Ph)(μ-PPh2)(PPh3)(CO)6] (2), and [Ru2(μ-η2-SC6H4PPh2)2(CO)4] (3) have been isolated. The SC6H4PPh2 ligand of compounds 1a and 1b has the sulfur atom spanning the same M–M edge as the hydride ligand and the phosphorus atom attached to one of the bridged metal atoms. Compound 2, which contains sulfide, phenyl, diphenylphosphanyl and triphenylphosphane ligands that arise from HSC6H4PPh2, has the Ru3 triangle capped by the sulfide and two Ru–Ru edges spanned by bridging phenyl and diphenylphosphanyl ligands. In complex 3, the two SC6H4PPh2 ligands have the same coordination behavior as in 1a or 1b; this binuclear complex is more conveniently prepared by treating [Ru2(μ-η2-MeCO2)2(CO)4(MeCN)2] with HSC6H4PPh2.