Isolation of a Cationic Platinum(II) sigma-Silane Complex

Abstract

The platinum complex [Pt(ItBuiPr¿)(ItBuiPr)][BArF] interacts with tertiary silanes to form stable (<0 C) mononuclear PtII sigma-SiH complexes [Pt(ItBuiPr¿)(ItBuiPr)(eta1-HSiR3)][BArF]. These compounds have been fully characterized, including X-ray diffraction methods, as the first examples for platinum. DFT calculations (including electronic topological analysis) support the interpretation of the coordination as an unusual eta1-SiH. However, the energies required for achieving a eta2-SiH mode are rather low, and is consistent with the propensity of these derivatives to undergo Si-H cleavage leading to the more stable silyl species [Pt(SiR3)(ItBuiPr)2]- [BArF] at room temperature.