Sigma Bond Metathesis Reactions of Si-H and M-Si Bonds. New Routes to d(0) Metal Silyl Complexes

摘要

The D metal silyl complexes CpCp*MSi(SiMe3)3 CL(1,Zr; 4,M= Hf; Cp= eta 5 -C5H5; Cp* = eta 5=C5Me5) react with PhSiH3 via a Sigma bond metathesis process to give CpCp *M(SiH2Ph)CL(2,M=Zr;5,M=Hf) and HSi(SiMe3)3. These reactions occur via both thermal and photochemical (normal fluorescent room light) pathways. The new silyl complexes 2 and 5 decompose thermally to the hydrides CpCp* MHC1n and polysilanes SiHPhm, but 5 was isolated and completely characterized. These q-bond metathesis reactions have been shown to provide general routes to a range of stable hafnium silyl complexes of the type CpCp*HfSiHRRc1, where - SiHRR is a primary or secondary silyl group. Keywords: Silicon Compounds, Methyl radicals, hafnium compounds, metal Complexes, Silanes, Reprints. (aw)