Silaallyl and Silylene Vinyl Complexes of CpW(CO)_2~+: Theoretical Study of their Bonding Nature and Comparison of Formation Reaction with Acetylide Analogue

摘要

Transition-metal complexes of pi-conjugate system including Si atom possess interesting electronic structure, bonding nature, reactivity, and similarities to and differences from the C analogues. Recently, Cp*(CO)_2W(C=CR)(SiPh_2) was experimentally isolated by Sakaba et al. and theoretically investigated by our group. In its formation reaction, silapropargyl species Cp*(CO)_2W(Si(Ph)_2C ident to CR) was experimentally proposed as an intermediate. Though this species has not been isolated yet, a similar W complex of eta~3-1-silaallyl group, Cp*(CO)_2W(Si(Me)_2CH=CR_2) A, was isolated experimentally. Also, Cp*(CO)_2W(C ident to CR)(SiPh_2) was isolated but its vinyl analogue Cp*(CO)_2W(CH=CR_2)(SiMe_2) B was not