Platinum(II) Hydride Silanone Complexes and Cyclic Trimers of Silanone. A Theoretical Study of Their Geometries, Bonding Nature, and Stabilities

Abstract

Platinum(II) hydride silanone complexes [PtH(dipe)(R2SiO)]+ (R = H, F, CH3, CF3, or SiH3; dipe = H2PCH2CH2PH2), their acetone and ethylene analogues, and cylic trimers of silanone, (R2SiO)3, were theoretically investigated with the DFT method. Unexpectedly, the platinum(II) hydride silanone complex does not involve a usual η2-SiO coordinate bond with the platinum center but two bonding interactions, one between the O atom and the platinum center and the other between the Si atom and the hydride ligand. The former interaction mainly consists of electron donation from a silanone π orbital to a Pt d orbital, while the latter one consists of back-donation from the hydride 1s orbital to the silanone π* orbital, as well as the electrostatic stabilization interaction between the Si atom and the hydride ligand. In the acetone analogue, on the other hand, only the O atom interacts with the platinum center, but the C atom does not interact with any part of [PtH(dipe)]+. The SiO bond lengthens by about 0.1 A and the...