Organometallic Complexes with Silicon-Transition Metal or Silicon-Carbon-Transition Metal Bonds

Abstract

This chapter provides a guide to the literature on organometallic complexes with silicon–transition metal (Si–M) or silicon–carbon–transition metal bonds (Si–C–M). It discusses complexes having Si–transition metal (M) bonds, the role of transition metal complexes in hydrosilylation, and complexes having Si–C–M bonds. The work of Hein and his associates on Sn–Co derivatives established the possibility of forming bonds between a Group IVB metal and a transition element, but it was another 15 years before CpFe(CO)2SiMe3—the first of many silyl derivatives—was synthesized. Substantial advances have been made in the field of hydrosilylation since 1965, when a comprehensive mechanism for catalysis by noble metal complexes was first published. The mechanism for the hydrosilylation of olefins catalyzed by chloroplatinic acid is outlined in the chapter. In 1970, two groups of workers independently drew attention to a type of alkyl ligand that was expected to have significance in transition-metal chemistry. This may formally be regarded as a carbanion in which one or more α-H atoms have been replaced by an organometallic or organic group. Six methods have been used for the synthesis of Me3SiCH2M and related complexes. All these have counterparts in Me–M and related chemistry.