Synthesis of metal complexes with highly reactive silicon species as ligands via Si-H bond activation and their reactivity

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1.Studies of synthesis, structure, and reactivity of silylene complexesBase-stabilized hydrido(silylene)tungsten complexes were synthesized via Si-H bond activation of di-and trihydrosilanes, and the following studies were carried out using these complexes. (1)Reaction of cis-Cp^*(CO)_2(H)W=SiHPh・Py (Cp^* = η^5-C_5Me_5) with phenylsilane gave the silyl(silylene) complex trans-Cp^* (CO)_2(PhH_2Si)W=SiHPh・Py, and the formation mechanism was elucidated. (2)Reaction of cis-Cp^*(CO)_2(H)W=SiPhR・L (R = Ph, H ; L = Py, THF) with anionic nucleophiles resulted in the formation of hydrido(silyl) complexes M^+[Cp^*(CO)_2(H)WSiPhRR']^-. Protonation of these anionic complexes gave dihydrido(silyl) complexes Cp^*(CO)_2(H)_2WSiPhRR', whose isomerization and dynamic processes in solution as well as crystal structures were revealed. (3)Hydrido(dichlorosilylene) complex cis-Cp^*(CO)_2(H)W=SiCl_2・Py was synthesized, and interligand hypervalent interaction was observed between the silicon and hydride ligands.2.Studies of synthesis and reactivity of η^3-silaallyl and η^3-silapropargyl complexesNovel η^3-silaallyl complexes Cp^*(CO)_2W(η^3-Me_2SiCR^1CR^2R^3) (R^1-R^3=H, Me) were synthesizes via Si-H bond activation of alkenylhydrosilanes, and their reactivity toward nucleophiles was mainly studied. In the reaction with methanol, silylalkene hydride complexes Cp^*(CO)_2(H)W(η^2-MeOMe_2SiCR^1=CR^2R^3) were formed, and the details of their insertion and isomerization processes were examined. In the Si-H bond activation reaction of alkynylhydrosilanes to synthesize η^3-silapropargyl complex, the unexpected complex Cp^*(CO)_2W(μ-η^1:η^2-C≡C^ΓBu)(SiPh_2) with an alkynyl ligand bridged to the tungsten and silicon atoms was isolated. This unique complex exhibited interesting reactivity toward polar reagents.