A DFT/Electron Localization Function (ELF) Study of the Bonding of Phosphinidenes with N-Heterocyclic Carbenes
| Autor: | Alain Sevin, Gilles Frison |
|---|---|
| Přispěvatelé: | Laboratoire de chimie théorique (LCT), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 1999 |
| Předmět: |
NUCLEOPHILIC CARBENE
010405 organic chemistry Chemistry Stereochemistry Transition metal carbene complex TOPOLOGICAL ANALYSIS Aromaticity PHOSPHAALKENES 010402 general chemistry Ring (chemistry) 01 natural sciences Acceptor Electron localization function 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry PHOSPHORUS Crystallography chemistry.chemical_compound ELF Phosphinidene ELECTRON LOCALIZATION FUNCTION Physical and Theoretical Chemistry Carbene AROMATICITY Pi backbonding |
| Zdroj: | Journal of Physical Chemistry A Journal of Physical Chemistry A, 1999, 103 (50), pp.10998-11003. ⟨10.1021/jp991550q⟩ Journal of Physical Chemistry A, American Chemical Society, 1999, 103 (50), pp.10998-11003. ⟨10.1021/jp991550q⟩ Scopus-Elsevier |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/jp991550q |
| Popis: | International audience; 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. |
| Databáze: | OpenAIRE |
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