Carbon–sulphur and carbon–hydrogen bond cleavages in the reactions of phenyl vinyl sulphide with triosmium clusters: crystal structure determination of [Os3(µ-SPh)(µ-CHCH2)(CO)10]

Abstract

Phenyl vinyl sulphide inserts at room temperature into an Os–H bond of [Os₃H₂(CO)₁₀] to give two diastereomers of the cluster [Os₃H (µ-PhSCHMe)(CO)₁₀]. However, under similar conditions the sulphide oxidatively adds to [Os₃(CO)₁₀(MeCN)₂] with C–S cleavage to give [Os₃(µ-SPh)(µ-CHCH₂)(CO)₁₀], the single-crystal X-ray structure of which has been determined. The structure relates to the known structure of [Os₃(µ-H)(µ-CHCH2)(CO)₁₀] except that the bridged Os–Os distance [3.328(1)Å] precludes a metal–metal bond. Thermolysis and photolysis products of [Os₃(µ-SPh)(µ-CHCH₂)(CO)₁₀] are formed by C–H cleavage at the aryl or vinyl groups: [Os₃H (SPh)(CCH₂)(CO)₉], [Os₄H(SPh)(CCH₂)(CO)₁₁], [Os₂(SPh)(CHCH₂)(CO)₆], [Os₃H(SPh)(CO)₁₀],[Os₃H(SC₆H₄)(CHCH₂)(CO)₉],[Os₃(SPh)(CMe)(CO)₉], [Os₂(SC₆H₄)(CHCH)(CO)₆], and [Os₃H₂(CCH₂)(CO)₉].