Cleavage of Si–H and Si–C Bonds by Metal–Ligand Cooperation: Formation of Silyl Anion and Silylene Equivalents from Tertiary Silanes

Abstract

The cleavage of silicon–hydrogen bonds to generate silicon-containing metal complexes has played an essential role in the preparation of organosilicon compounds. Herein, we report the reaction of cyclopentadienone iridium complex 1 with hydrosilanes to afford hydroxycyclopentadienyl iridium silyl complexes 4 via the umpolung of the Si–H bond. The nucleophilicity of the Ir–Si bond in the resulting complex was demonstrated in the reaction with an allyl halide and ethyl acrylate. Furthermore, a silylene complex was formed from hydroxycyclopentadienyl silyliridium complex 4 via the formal reductive elimination of the C–H bond at the silicon center to release benzene. The silylene complex synthesized from tricarbylsilane showed ambiphilic reactivities, which are consistent with the classical reactivities of silylenes.