Facile Access to Dative, Single, and Double Silicon-Metal Bonds Through M-Cl Insertion Reactions of Base-Stabilized Si Cations.

Silicon(II) cations can offer fascinating reactivity patterns due to their unique electronic structure: a lone pair of electrons, two empty p orbitals and a positive charge combined on a single silicon center. We now report the facile insertion of N-heterocyclic carbene (NHC)-stabilized silyliumylidene ions into M-Cl bonds (M=Ru, Rh), forming a series of novel chlorosilylene transition-metal complexes. Theoretical investigations revealed a reaction mechanism in which the insertion into the M-Cl bond with concomitant 1,2-migration of a silicon-bound NHC to the transition metal takes place after formation of an initial silyliumylidene transition-metal complex. The mechanism could be verified experimentally through characterization of the intermediate complexes. Furthermore, the obtained chlorosilylene complexes can be conveniently utilized as synthons to access Si-M and Si=M bonding motifs bonds through reductive dehalogenation.