Reactivity of 2-(diphenylphosphanyl)thiophenol (HSC6H4PPh2) with rutheniumand osmium carbonyl complexes; Breaking of HSC6H4PPh2 into sulfide, phenyland diphenylphosphanyl ligands on a triruthenium cluster

2-(Diphenylphosphanyl)thiophenol (HSC6H4PPh2) reacts with the carbonyl clus ters [Ru-3(CO)(12)] and [Os-3(CO)(10)(MeCN)(2)] to give mixtures of product s, the composition of which depends upon the reaction conditions and the ra tio of the reactants. The derivatives [M-3(mu-H)(mu-eta(2)-SC6H4PPh2)(CO)(9 )] (1a: M = Ru; 1b: M = Os), [Ru-3(mu(3)-S)(mu-eta(2)-Ph) (mu-PPh2) (PPh3) (CO)(6)] (2), and [Ru-2(mu-eta(2)- SC6H4PPh2)(2)(CO)(4)] (3) have been isol ated. The SC6H4PPh2 ligand of compounds 1a and 1b has the sulfur atom spann ing the same M-M edge as the hydride ligand and the phosphorus atom attache d to one of the bridged metal atoms. Compound 2, which contains sulfide, ph enyl, diphenylphosphanyl and triphenylphosphane ligands that arise from HSC 6H4PPh2, has the Ru-3 triangle capped by the sulfide and two Ru-Ru edges sp anned by bridging phenyl and diphenylphosphanyl ligands. In complex 3, the two SC6H4PPh2 ligands have the same coordination behavior as in 1a or 1b; t his binuclear complex is more conveniently prepared by treating [Ru-2(mu-et a(2)-MeCO2)(2)(CO)(4)(MeCN)(2)] with HSC6H4PPh2.