Rhodium(III)-NSi Catalyzed Styrene Hydrosilylation: Evidence of the Hemilabile Character of NSi-type Ligands.

The 18e saturated rhodium(III) species [Rh(H)(X)(κ2-NSitBu2)(bipyMe2)] (NSitBu2 = {4-methylpyridine-2-yloxy}ditertbutylsilyl; bipyMe2 = 4,4´-dimethylbipyridine) (X = Cl, 1; OTf, 2) have been prepared and characterized by NMR spectroscopy and in the case of 2 it has been possible to determine its solid-state structure by X-ray diffraction. Complex 1 has proven to be an effective catalyst precursor for the reaction of styrene derivatives with hydrosilanes in CD2Cl2. However, under catalytic conditions complex 2 decomposes.