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DOI: 10.1039/A904793J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3487-3491

A density functional study of [M(PH3)2(η2-C2X4)] alkene complexes for the Group 10 metals Ni, Pd, Pt: the effect of electron-attracting substituents

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Francesco Nunzi, Antonio Sgamellotti, Nazzareno Re and Carlo Floriani

Abstract

Density functional calculations have been performed for [M(PH3)2(C2X4)] complexes with M = Ni, Pd or Pt and X = H, F or CN to study the effect of electron-attracting substituents on the metal–olefin bonding. The optimised geometries have been found to be in good agreement with experimental crystal structure data. The electronic structure has been analysed in terms of the Chatt–Dewar–Duncanson model and the contribution from π back donation was found to dominate over that from σ donation for both ethylene and substituted ethylene complexes. Reliable values have been calculated for the metal–olefin bond dissociation energies and compared with the available experimental data.

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