Hydrosilylation of Ketones, Imines and Nitriles Catalysed by Electrophilic Phosphonium Cations: Functional Group Selectivity and Mechanistic Considerations. Issue 17 (10th March 2015) - Pérez, Manuel
Abstract 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.