-Functionalised NHC Ligands for Efficient Nickel-catalysed C-O Hydrosilylation.

A series of C,O-bidentate chelating mesoionic carbene nickel(ii) complexes [Ni(NHC^PhO)₂] (NHC = imidazolylidene or triazolylidene) were applied for hydrosilylation of carbonyl groups. The catalytic system is selective towards aldehyde reduction and tolerant to electron-donating and -withdrawing group substituents. Stoichiometric experiments in the presence of different silanes lends support to a metal-ligand cooperative activation of the Si-H bond. Catalytic performance of the nickel complexes is dependent on the triazolylidene substituents. Butyl-substituted triazolylidene ligands impart turnover numbers up to 7,400 and turnover frequencies of almost 30,000 h, identifying this complex as one of the best-performing nickel catalysts for hydrosilylation and demonstrating the outstanding potential of -functionalised NHC ligands in combination with first-row transition metals.