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D. Sturmayr, U. Schubert:
"A Comparison of the Reactivity of Chloroalkanes and Chlorosilanes towards Activated Pt^II Complexes by DFT Calculations";
European Journal of Inorganic Chemistry, 4 (2004), 776 - 782.

The pathways of the C-Cl bond activation of CCl₄ and CH₃Cl by the 14-electron Pt^II complexes [PtMe₂(PH₃)] or the corresponding reactions of SiCl₄ and SiH₃Cl with [PtMe(SiH₃)(PH₃)] were investigated by DFT calculations. The complexes [Pt(EH₃)Me(PH₃)] (E = C, Si) are models for [Pt(EH₃)Me{(κ²-P,N)-Ph₂PCH₂CH₂NMe₂}], with hemilabile P,N chelating ligands, used in practical experiments. While the reaction of [Pt(EH₃)Me(PH₃)] with ECl₄ results in an EH₃/ECl₃ exchange, reaction of [Pt(EH₃)Me(PH₃)] with EH₃Cl results in the elimination of E₂H₆. Both reactions proceed via a five-coordinate Pt^IV intermediate. The elimination of Si₂H₆ is endothermic.

http://aleph.ub.tuwien.ac.at/F?base=tuw01&func=find-c&ccl_term=AC04969074

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