4.5 Article

A Contribution to the Direct Observation of Transient Phosphanylidene Complexes [ RP= W( CO)5] ( R: Me, Ph): A Revisited Approach to Their Electronic Structure by UV-Photoelectron Spectroscopy

Journal

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume 2014, Issue 10, Pages 1694-1705

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201301033

Keywords

Electronic structure; Photoelectron spectroscopy; Density functional calculations; Carbene homologues; Phosphorus

Funding

  1. Centre National de la Recherche Scientifique (CNRS)
  2. Universite de Pau et des Pays de l'Adour (UPPA)
  3. Ministere de la Recherche

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An original approach involving a coupling in the gas phase between flash vacuum thermolysis (FVT) and UV-photoelectron spectroscopy (UV-PES) allowed the transient terminal electrophilic phosphanylidene complex [MeP=W(CO)(5)] to be characterized; this is the first direct observation of this P-Me derivative. This approach also permitted the electronic structure of [PhP=W(CO)(5)] to be revisited and confirmed the results obtained with the methylated analogues. In contrast, [p-NC-C6H4P=W(CO)(5)] proved to be too reactive to be detected under our experimental conditions. These [RP=W(CO)(5)] phosphanylidene complexes (R: Me, Ph) were identified by their ionization potentials, which are real fingerprints. These experimental data, supported by density functional calculations, give an overall electronic cartography of these transient species. For generation in the gas phase of these phosphanylidene complexes, the thermal degradation of two kinds of precursors were investigated. The joint experimental/theoretical approach allowed us to conclude that phosphanorbornadiene complexes are more suitable precursors than phosphirane complexes.

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