DFT Calculations on the C−Cl/Si−H Exchange Catalyzed by P , N ‐Chelated Pt II Complexes

The mechanism of the previously reported C−Cl/Si−H exchange reaction between H x CCl 4− x ( x = 0−3) and HSiMe 2 Ph catalyzed by [PtMeCl(Ph 2 PCH 2 CH 2 NMe 2 ‐κ 2 P , N )] [PtMeCl(P∩N)] was investigated by DFT calculations. The energetically less‐favored isomer of [PtMeCl(P∩N)], with Cl and P being cis , was identified to be the actual catalytic species. The catalytic reaction proceeds by oxidative addition of the silane, de‐coordination of the nitrogen atom of the P , N ‐chelating ligand, reductive elimination of the chlorosilane and oxidative addition of the C−Cl bond of H x CCl 4− x . The final step is the reductive elimination of the C−H bond with concomitant re‐coordination of the nitrogen atom of the P , N ‐chelating ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)