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

The platinum complex [Pt(I Bu Pr')(I Bu Pr)][BAr ] interacts with tertiary silanes to form stable (<0 °C) mononuclear Pt σ-SiH complexes [Pt(I Bu Pr')(I Bu Pr)(η -HSiR )][BAr ]. 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 η -SiH. However, the energies required for achieving a η -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(SiR )(I Bu Pr) ][BAr ] at room temperature.