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

Abstract

The low-electron-count cationic platinum complex [Pt(ItBu’)(ItBu)][BAr], 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 η-SiH. The reaction of 1 with EtSiH leads to the X-ray structurally characterized 14-electron Pt species [Pt(SiEtH)(ItBu)][BAr], 2, which is stabilized by an agostic interaction. Complexes 1, 2, and the hydride [Pt(H)(ItBu)][BAr], 3, catalyze the hydrosilation of CO, leading to the exclusive formation of the corresponding silyl formates at room temperature.