A DFT/Electron Localization Function (ELF) Study of the Bonding of Phosphinidenes with N-Heterocyclic Carbenes

Gilles Frison 1, * Alain Sevin 1
Abstract : The bonding between model phosphinidene PH and two types of cyclic Arduengo's carbenes, the aromatic C3H4N2 (1) and the related saturated C3H6N2 (2) species, respectively, have been analyzed in terms of the electron localization function (ELF). In a first step, the bare carbenes have been studied, and then, in a second step, the changes brought about by PH complexation have been treated. It has been shown that the bonding mode essentially results from a dative bond formed by the nucleophilic carbenic carbon of the ring and the PH acceptor site. Some back bonding from P creates a partial double-bond character around the C-P unit. The latter character is more pronounced when PH is linked to the saturated carbene 2. A comparison of the ring aromatic properties, in terms of nucleus-independent chemical shifts has been achieved, showing that complexation of 1 by PH diminishes the ring aromaticity through relocalization of the electrons on the N atoms.
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Soumis le : mardi 9 mars 2010 - 23:31:47
Dernière modification le : jeudi 21 mars 2019 - 14:52:56

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Gilles Frison, Alain Sevin. A DFT/Electron Localization Function (ELF) Study of the Bonding of Phosphinidenes with N-Heterocyclic Carbenes. Journal of Physical Chemistry A, American Chemical Society, 1999, 103 (50), pp.10998-11003. ⟨10.1021/jp991550q⟩. ⟨hal-00462491⟩

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