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

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