Synthesis and Characterization of Single Thiolato-Bridged Heterodinuclear Complexes: Irreversible Isomerization of Cp(CO)₂W(μ-SPh)(μ-Cl)Ru(CO)(Cl)(PPh₃) to Cp(CO)(Cl)W(μ-SPh)(μ-Cl)Ru(CO)₂(PPh₃) via Chloride and Carbonyl Ligand Migration

Reaction between CpW(CO)3SPh and RuCl2(PPh3)x (x = 3 and 4) in dichloromethane at room temperature afforded a single thiolato-bridged heterodinuclear complex, Cp(CO)2W(μ-SPh)(μ-Cl)Ru(CO)(Cl)(PPh3) (1) in high yield. Irreversible isomerization of 1 to Cp(CO)(Cl)W(μ-SPh)(μ-Cl)Ru(CO)2(PPh3) (2), which exists as a mixture of stereoisomers 2a and 2b, occurs via chloride and carbonyl ligand migration during thermolysis of 1 in toluene at 80 °C. Compounds 1, 2a, and 2b were characterized by single-crystal X-ray diffraction analysis. Migration of π-acceptor carbonyl ligands from W atom to Ru atom during the conversion of CpW(CO)3SPh + RuCl2(PPh3)3 → 1 → 2 with concomitant migration of σ-donor chloride ligand from Ru to W atom in 1 is reported.