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

© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The platinum complex [Pt(ItBuiPr′)(ItBuiPr)][BArF] interacts with tertiary silanes to form stable (<0 °C) mononuclear PtII σ-SiH complexes [Pt(ItBuiPr′)(ItBuiPr)(η1-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 η1-SiH. However, the energies required for achieving a η2-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.