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. Issue 10 (24th September 2013)

• Record Type: Journal Article
• Authors: Labat, Stéphane; Miqueu, Karinne; Sotiropoulos, Jean‐Marc; Baylère, Patrick; Pfister‐Guillouzo, Geneviève; Huy, Ngoc Hoa Tran; Mathey, François
• Other Names: Caporali Maria sponsoringEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 10(2014)
• Page Start: 1694
• Page End: 1705
• Publication Date: 2013-09-24
• Subjects: Electronic structure -- Photoelectron spectroscopy -- Density functional calculations -- Carbene homologues -- Phosphorus; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201301033
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: 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–C6 H4 P=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. Abstract : By using an original coupling involving FVT and UV‐photoelectron spectroscopy, the electronic structure of the transient electrophilic phosphanylidene complex [MeP=W(CO)5 ] has been described for the first time and that of [PhP=W(CO)5 ] has been revisited. These intermediates were generated in the gas phase and unambiguously characterized by their ionization potentials, real "fingerprints".