An in-depth investigation of the reaction of tertiary hydrosilanes with [CpW(CO)2(IMes)] + [B(C6F5)4] − reveals a fundamentally new Si-H bond activation mode. Unlike the originally proposed oxidative addition of the Si-H bond to the tungsten(II) center, there is strong experimental and NMR spectroscopic evidence for the involvement of one of the CO ligands of the cationic complex in the Si-H bond breaking event. The Si-H bond is heterolytically cleaved to form a tungsten(II) hydride and a silylium ion, which is stabilized by one of the CO ligands. This reactive hydrosilane adduct was eventually isolated and characterized by X-ray diffraction analysis. Quantum-chemical calculations support a cooperative mechanism but a stepwise process consisting of oxidative addition and subsequent tungsten-to-oxygen silyl migration in the tungsten(IV) silyl hydride is also energetically feasible. However, our combined spectroscopic and computational analysis favors the cooperative pathway. The newly identified hydrosilane adduct is the key intermediate of Bullock's ionic carbonyl hydrosilylation.

An experimental analysis proves that Nikonov’s carbonyl hydrosilylation proceeds through a two-silicon cycle rather than the originally proposed one-silicon cycle. The intermediate ruthenium­(II) monohydride is not sufficiently hydridic to transfer its hydride onto the silylcarboxonium ion. However, that hydricity is enhanced by oxidative addition of another hydrosilane molecule to afford the corresponding ruthenium­(IV) silyl dihydride as the actual hydride donor. The present study also demonstrates that the acetonitrile ligands in Nikonov’s ruthenium­(II) catalyst are not innocent. That complex is able to hydrosilylate its own ligand(s), and the resulting N,N-disilylated amine base accounts for competing dehydrogenative silylation of enolizable carbonyl compounds, explaining the formation of a silyl enol ether in substantial quantities next to the expected silyl ether. Both findings lead to a revised mechanistic picture that provides the basis for the development of more efficient and chemoselective catalysts.