A Comparison of the Reactivity of Chloroalkanes and Chlorosilanes towards Activated Pt II Complexes by DFT Calculations

The pathways of the C−Cl bond activation of CCl 4 and CH 3 Cl by the 14‐electron Pt II complexes [PtMe 2 (PH 3 )] or the corresponding reactions of SiCl 4 and SiH 3 Cl with [PtMe(SiH 3 )(PH 3 )] were investigated by DFT calculations. The complexes [Pt(EH 3 )Me(PH 3 )] (E = C, Si) are models for [Pt(EH 3 )Me{(κ 2 ‐ P , N )‐Ph 2 PCH 2 CH 2 NMe 2 }], with hemilabile P,N chelating ligands, used in practical experiments. While the reaction of [Pt(EH 3 )Me(PH 3 )] with ECl 4 results in an EH 3 /ECl 3 exchange, reaction of [Pt(EH 3 )Me(PH 3 )] with EH 3 Cl results in the elimination of E 2 H 6 . Both reactions proceed via a five‐coordinate Pt IV intermediate. The elimination of Si 2 H 6 is endothermic. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)