Reactions of [HOs3(CO)10(µ-L)] (L = saccharinate, thiosaccharinate) with Ph3SnH and Ph3GeH

Abstract

Reactions of triosmium clusters bearing a bridging saccharinate (sac) or thiosaccharinate (tsac) ligand with Ph3EH (E = Sn, Ge) are examined. The saccharinate cluster [HOs3(CO)10(µ-N,O-sac)] reacts with Ph3EH at 110°C to yield [H2Os3(CO)9(EPh3)(µ-N,O-sac)] (1a, E = Sn; 1b, E = Ge) through oxidative-addition of E‒H bond to the parent cluster. Similar reaction between the thiosaccharinate cluster [HOs3(CO)10(µ-N,S-tsac)] and Ph3EH at 98°C affords [H2Os3(CO)9(EPh3)(µ-N,S-tsac)] (2a, E = Sn; 2b, E = Ge) and [H2Os3(CO)8(EPh3)(µ-N,C-C6H4CNSO2)(µ3-S)] (3a, E = Sn; 3b, E = Ge), the latter being isolated as the major product. Control experiments show that competitive pathways are involved in this reaction, and the products are formed via separate reaction pathways. Another product namely [Os3(CO)9(µ3-N,C-C6H4CHNSO2)(µ3-S)] (4) was also isolated from the reaction between [HOs3(CO)10(µ-N,S-tsac)] and Ph3GeH which does not contain any germanium ligand, and is directly formed from the parent tsac-substituted cluster as confirmed by independent control experiments. The molecular structures of the different types of products isolated from these reactions have been confirmed by single crystal X-ray diffraction analyses.