Mode of Activation of Cobalt(II) Amides for Catalytic Hydrosilylation of Alkenes with Tertiary Silanes.

Cobalt(II) complexes capable of catalyzing alkene hydrosilylation in the absence of external activators are rarely known, and their activation mode has remained poorly understood. We present here that cobalt(II) amide complexes, [Co(N(SiMe3)2)2] and its NHC adducts [(NHC)Co(N(SiMe3)2)2] (NHC = N-heterocyclic carbene), are effective catalysts for the hydrosilylation of alkenes with tertiary silanes. Mechanistic studies revealed that cobalt(II) amides can react with hydrosilane to form cobalt(I) species, silylamide, and hydrogen, which serves as the entry to the genuine catalytically active species, presumably cobalt(I) species, for the cobalt-catalyzed hydrosilylation reaction.