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

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 PtII 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.