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DFT Calculations on the C−Cl/Si−H Exchange Catalyzed by P , N ‐Chelated Pt II Complexes
Author(s) -
Sturmayr Dietmar,
Schubert Ulrich
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400029
Subject(s) - chemistry , chlorosilane , oxidative addition , catalysis , reductive elimination , ligand (biochemistry) , chelation , medicinal chemistry , silane , nitrogen , stereochemistry , inorganic chemistry , organic chemistry , silicon , biochemistry , receptor
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)