Synthesis and structural characterisation of some new triosmium alkylidyne clusters containing sulfur-donor ligands. The formation of C–S and C–C bonds

Abstract

The neutral clusters [Os3(µ-H)2(CO)9{µ-C[graphic omitted]H2}]1 and [Os3(µ-H)2(CO)9{µ3-C[graphic omitted]H2}]2 were synthesised in good to moderate yields respectively by the reaction of [Os3(µ-H)3(CO)9(µ3-CCl)] with 1 equivalent of 1,8-diazabicyclo[5.4.0]undec-7-ene, in the presence of a 10-fold excess of thiane or 1,4-dithiane. Under ambient conditions, complex 2 in solution slowly rearranges to a novel ketenylidene-bridged cluster [Os3(µ-H)2(CO)8{[graphic omitted]H2}(µ3-CCO)]3, which is formed by exchange of [graphic omitted]H2 and CO at the µ3-carbon. All complexes were fully characterised by spectroscopic methods and their molecular structures established by single-crystal X-ray analyses.