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

Abstract

The platinum complex [Pt(I^t Buⁱ Pr')(I^t Buⁱ Pr)][BAr^F ] interacts with tertiary silanes to form stable (<0 °C) mononuclear Pt^II σ-SiH complexes [Pt(I^t Buⁱ Pr')(I^t Buⁱ Pr)(η¹ -HSiR₃ )][BAr^F ]. 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 )(I^t Buⁱ Pr)₂ ][BAr^F ] at room temperature.

Keywords: density-functional calculations; platinum; silane; structure elucidation; x-ray diffraction.