Disilametallacycles as a Platform for Stabilizing M(II) and M(IV) (M = Fe, Ru) Centers: Synthesis and Characterization of Half-Sandwich Complexes and Their Application to Catalytic Double Silylation of Alkenes and Alkynes

Abstract

A series of group 8 half-sandwich disilametallacycles, (η6-arene)MII(Me2SiC6H4SiMe2)L and (η6-arene)MIV(H)2(Me2SiC6H4SiMe2) (M = Fe, Ru) in the formal oxidation states of M(II) and M(IV) were synthesized and characterized. Both the M(II) and the M(IV) oxidation states were effectively stabilized by the disilametallacycle skeleton, and facile interconversion between (η6-arene)MII–dinitrogen, (η6-arene)MII–carbonyl, and (η6-arene)MIV–dihydride complexes bearing a disilaferracycle framework was accomplished. These M(II) and M(IV) complexes can easily generate coordinatively unsaturated 16e disilametallacycles, (η6-arene)MII(Me2SiC6H4SiMe2), by dissociation of L or H2, and stoichiometric and/or catalytic double silylation of alkenes and alkynes was realized thorough this 16e intermediate.