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

IIQ

Pablo Ríos, Hugo Fouilloux, Pietro Vidossich, Josefina Díez, Agustí Lledós, and Salvador Conejero Angew. Chem. Int. Ed. 2018, Vol. 57, 3217 –3221

The platinum complex [Pt(I^tBuⁱPr′)(I^tBuⁱPr)][BAr^F] interacts with tertiary silanes to form stable (<0 °C) mononuclear Pt^II σ‐SiH complexes [P^t(ItBuⁱPr′)(I^tBuⁱPr)(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^tBuⁱPr)₂][BAr^F] at room temperature.

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