Hydrosilylation of Ketones, Imines and Nitriles Catalysed by Electrophilic Phosphonium Cations: Functional Group Selectivity and Mechanistic Considerations

Abstract

Abstract The electrophilic phosphonium salt, [(C 6 F 5 ) 3 PF][B(C 6 F 5 ) 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. [(C 6 F 5 ) 3 PCl][B(C 6 F 5 ) 4 ] and [(C 6 F 5 ) 3 PBr][B(C 6 F 5 ) 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.