Cleavage of Ge–S and C–H bonds in the reaction of electron-deficient [Os3(CO)8(μ-H)(μ3-Ph2PCH2P(Ph)C6H4)] with Ph3GeSPh: Generation of thiophenol derivatives [Os3(CO)8(μ-H)(μ-SPh)(μ-dppm)] and [Os3(CO)7(μ-H)(μ-SPh)(μ3-SC6H4)(μ-dppm)]

Heating the electron-deficient [Os3(CO)8(μ-H)(μ3-Ph2PCH2P(Ph)C6H4)] (1) and Ph3GeSPh in benzene at 80 °C led to the thiolato bridged compounds, [Os3(CO)8(μ-H)(μ-SPh)(μ-dppm)] (2) and [Os3(CO)7(μ-H)(μ-SPh)(μ3-SC6H4)(μ-dppm)] (3), formed by cleavage of Ge–S and C–S bonds of the ligand, in 40% and 17% yields, respectively. Both compounds 2 and 3 have been characterized by a combination of elemental analysis, infrared and 1H NMR spectroscopic data together with single crystal X-ray crystallography. Compound 3 contains an open triangle of osmium atoms bridged by a SPh and SC6H4 ligands on opposite sides of the cluster with a dppm ligand bridging one of the Os–Os edges. Compound 2 consists of a closed triangular cluster of osmium atoms with a bridging SPh, and a bridging hydride ligand on the same Os–Os edge, and a dppm ligand bridging one of the remaining Os–Os edges.

Reaction of the electron-deficient [Os3(CO)8(μ-H)(μ3-Ph2PCH2P(Ph)C6H4)] (1) with Ph3GeSPh at 80 °C led to two triosmium compounds, [Os3(CO)8(μ-H)(μ-SPh)(μ-dppm)] (2) and [Os3(CO)7(μ-H)(μ-SPh)(μ3-SC6H4)(μ-dppm)] (3). Compound 3 represents a rare example of a structurally characterized orthometallated arylthiolate ligand on a triosmium cluster.Figure optionsDownload as PowerPoint slide