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. 2016 Nov 14;22(47):16791-16795.
doi: 10.1002/chem.201603524. Epub 2016 Oct 11.

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

Pablo Ríos  1 , Josefina Díez  2 , Joaquín López-Serrano  1 , Amor Rodríguez  1 , Salvador Conejero  1
Affiliations

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

Pablo Ríos et al. Chemistry. .

Abstract

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 Et2 SiH2 leads to the X-ray structurally characterized 14-electron PtII species [Pt(SiEt2 H)(ItBu)2 ][BArF ], 2, which 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.

Keywords: carbon dioxide; hydrosilation; platinum; silane; σ-complex.

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