Cationic Bis(hydrosilane)—Coinage‐Metal Complexes: Synthesis, Characterization, and Use as Catalysts for Outer‐Sphere C=O Hydrosilylation Not Involving Metal Hydrides

Abstract

The preparation of cationic bis(hydrosilane)–coinage‐metal complexes by chloride abstraction from the neutral metal chloride precursors with Na[BArF4] is described. Unlike previously reported hydrosilane‐stabilized copper and silver complexes, the presented complexes are cationic and feature two bidentate ortho‐(silylphenyl)phosphine ligands. These complexes were fully characterized by NMR spectroscopy and X‐ray diffraction analysis, revealing that both Si–H bonds are activated by the Lewis acidic cationic metal center. The new complexes were found to be effective in catalytic carbonyl hydrosilylation, leading to the corresponding silyl ethers under mild conditions without the addition of an external base. Combined mechanistic control experiments and quantum chemical calculations support an ionic outer‐sphere mechanism, in which a neutral metal alkoxide species instead of a metal hydride is the key intermediate that interacts with the silylcarboxonium ion to generate the silyl ether.