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

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 deriva...

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Main Authors: Labat, Stéphane, Miqueu, Karinne, Sotiropoulos, Jean-Marc, Baylère, Patrick, Pfister-Guillouzo, Geneviève, Huy, Ngoc Hoa Tran, Mathey, François
Other Authors: School of Physical and Mathematical Sciences
Format: Article
Language:English
Published: 2014
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Online Access:https://hdl.handle.net/10356/99273
http://hdl.handle.net/10220/19628
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-992732020-03-07T12:37:07Z 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 Labat, Stéphane Miqueu, Karinne Sotiropoulos, Jean-Marc Baylère, Patrick Pfister-Guillouzo, Geneviève Huy, Ngoc Hoa Tran Mathey, François School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Inorganic chemistry::Analysis 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. 2014-06-10T06:55:52Z 2019-12-06T20:05:16Z 2014-06-10T06:55:52Z 2019-12-06T20:05:16Z 2014 2014 Journal Article Labat, S., Miqueu, K., Sotiropoulos, J.-M., Baylère, P., Pfister-Guillouzo, G., Huy, N. H. T., et al. (2014). 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. European Journal of Inorganic Chemistry, 2014(10), 1694-1705. 1434-1948 https://hdl.handle.net/10356/99273 http://hdl.handle.net/10220/19628 10.1002/ejic.201301033 en European journal of inorganic chemistry © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
institution Nanyang Technological University
building NTU Library
country Singapore
collection DR-NTU
language English
topic DRNTU::Science::Chemistry::Inorganic chemistry::Analysis
spellingShingle DRNTU::Science::Chemistry::Inorganic chemistry::Analysis
Labat, Stéphane
Miqueu, Karinne
Sotiropoulos, Jean-Marc
Baylère, Patrick
Pfister-Guillouzo, Geneviève
Huy, Ngoc Hoa Tran
Mathey, François
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
description 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.
author2 School of Physical and Mathematical Sciences
author_facet School of Physical and Mathematical Sciences
Labat, Stéphane
Miqueu, Karinne
Sotiropoulos, Jean-Marc
Baylère, Patrick
Pfister-Guillouzo, Geneviève
Huy, Ngoc Hoa Tran
Mathey, François
format Article
author Labat, Stéphane
Miqueu, Karinne
Sotiropoulos, Jean-Marc
Baylère, Patrick
Pfister-Guillouzo, Geneviève
Huy, Ngoc Hoa Tran
Mathey, François
author_sort Labat, Stéphane
title 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
title_short 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
title_full 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
title_fullStr 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
title_full_unstemmed 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
title_sort 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
publishDate 2014
url https://hdl.handle.net/10356/99273
http://hdl.handle.net/10220/19628
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