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Cationic Platinum(II) sigma-SiH Complexes in Carbon Dioxide Hydrosilation

IIQ

P. Ríos, J. Díez, J. López-Serrano, A. Rodríguez, S. Conejero Chemistry: A European Journal 2017, Vol. 22, 16791-19795

The low electron count cationic platinum complex [Pt(ItBu’)(ItBu)][BArF], 1, interacts with primary and secondary silanes to form the corresponding σ-SiH complexes. According to DFT calculations the most stable coordination mode is the uncommon η1-SiH. The reaction of 1 with Et2SiH2 leads to the X-ray structurally characterized 14-electron Pt(II) species [Pt(SiEt2H)(ItBu)2][BArF], 2,that is stabilized by an agostic interaction. Complexes 1, 2 and the hydride [Pt(H)(ItBu)2][BArF], 3, catalyze the hydrosilation of CO2 leading to the exclusive formation of the corresponding silyl formates at room temperature.