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

作者：Labat Stephane; Miqueu Karinne^*; Sotiropoulos Jean Marc; Baylere Patrick; Pfister Guillouzo Genevieve; Ngoc Hoa Tran Huy; Mathey Francois

来源：European Journal of Inorganic Chemistry, 2014, 2014(10): 1694-1705.

DOI：10.1002/ejic.201301033

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

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.

• 出版日期2014-4
• 单位南阳理工学院