A cyclopentadienyl functionalized silylene-a flexible ligand for Si- And C-coordination

Abstract

The synthesis of a 1,2,3,4-tetramethylcyclopentadienyl (Cp$^{4}$) substituted four-membered N-heterocyclic silylene [{PhC(NtBu) $_{2}$}Si(C$_{5}$Me$_{4}$H)] is reported first. Then, selected reactions with transition metal and a calcium precursor are shown. The proton of the Cp$_{4}$-unit is labile. This results in two different reaction pathways: (1) deprotonation and (2) rearrangement reactions. Deprotonation was achieved by the reaction of [{PhC(NtBu) $_{2}$}Si(C$_{5}$Me$_{4}$H)] with suitable zinc precursors. Rearrangement to [{PhC(NtBu) $_{2}$}(C$_{5}$Me$_{4}$)SiH], featuring a formally tetravalent silicon R$_{2}$CSi(R′)-H unit, was observed when the proton of the Cp$^{4}$ ring was shifted from the Cp$^{4}$-ring to the silylene in the presence of a Lewis acid. This allows for the coordination of the Cp$^{4}$-ring to a calcium compound. Furthermore, upon reaction with transition metal dimers [MCl(cod)] $_{2}$ (M = Rh, Ir; cod = 1,5-cyclooctadiene) the proton stays at the Cp$^{4}$-ring and the silylene reacts as a sigma donor, which breaks the dimeric structure of the precursors