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 [Os-3(CO)(8)(mu-H)(mu(3)-Ph2PCH2P(Ph)C6H4)] (1) and Ph3GeSPh in benzene at 80 degrees C led to the thiolato bridged compounds, [Os-3(CO)(8)(mu-H)(mu-SPh)(mu-dppm)] (2) and [Os-3(CO)(7)(mu-H)(mu-SPh)(mu(3)-SC6H4)(mu-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 H-1 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. (C) 2008 Elsevier B.V. All rights reserved.