Hydrosilylation of ketones, imines and nitriles catalysed by electrophilic phosphonium cations: Functional group selectivity and mechanistic considerations

The electrophilic phosphonium salt, [(C₆F₅)₃PF][B(C₆F₅)₄], catalyses the efficient hydrosilylation of ketones, imines and nitriles at room temperature. In the presence of this catalyst, adding one equivalent of hydrosilane to a nitrile yields a silylimine product, whereas adding a second equivalent produces the corresponding disilylamine. [(C₆F₅)₃PCl][B(C₆F₅)₄] and [(C₆F₅)₃PBr][B(C₆F₅)₄] are also synthesised and tested as catalysts. Competition experiments demonstrate that the reaction exhibits selectivity for the following functional groups in order of preference: ketone>nitrile>imine>olefin. Computational studies reveal the reaction mechanism to involve initial activation of the Si-H bond by its interaction with the phosphonium centre. The activated complex then acts cooperatively on the unsaturated substrate. Proceed with cation: The electrophilic phosphonium salt, [(C₆F₅)₃PF][B(C₆F₅)₄], catalyses the efficient hydrosilylation of ketones, imines and nitriles at room temperature. In the presence of this catalyst, adding one equivalent of hydrosilane to a nitrile yields a silylimine product, whereas adding a second equivalent produces the corresponding disilylamine.