Abstract
Reactions of the di(tert-butylphosphino)ethane complex (dtbpe)Rh(CH2Ph) with Ph2SiH2 and Et2SiH2 resulted in isolation of (dtbpe)Rh(H)2(SiBnPh2) (1; Bn = CH2Ph) and (dtbpe)Rh(H)2(SiBnEt2) (2), respectively. Both 1 and 2 feature strong interactions between the rhodium hydride and silyl ligands, as indicated by large 2JSiH values (44.4 and 52.1 Hz). The reaction of (dtbpm)Rh(CH2Ph) (dtbpm = di(tert-butylphosphino)methane) with Mes2SiH2 gave the pseudo-three-coordinate Rh complex (dtbpm)Rh(SiHMes2) (3), which is stabilized in the solid state by agostic interactions between the rhodium center and two C–H bonds of a methyl substituent on the mesityl group. The analogous germanium compound (dtbpm)Rh(GeHMes2) (4) is also accessible. Complex 3 readily undergoes reactions with diphenylacetylene, phenylacetylene, and 2-butyne to give the silaallyl complexes (dtbpm)Rh[Si(CPh═CHPh)Mes2] (5), (dtbpm)Rh[Si(CH═CHPh)Mes2] (7), and (dtbpm)Rh(Si(CMe═CHMe)Mes2) (8) via net insertions into the Si–H bond. The germaallyl compl...
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