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...
| Main Authors: | , , , , , , |
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| Format: | Journal Article |
| Language: | English |
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2014
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| Online Access: | https://hdl.handle.net/10356/99273 http://hdl.handle.net/10220/19628 |
| _version_ | 1811692855942447104 |
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| author | Labat, Stéphane Miqueu, Karinne Sotiropoulos, Jean-Marc Baylère, Patrick Pfister-Guillouzo, Geneviève Huy, Ngoc Hoa Tran Mathey, François |
| 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 |
| author_sort | Labat, Stéphane |
| collection | NTU |
| 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. |
| first_indexed | 2024-10-01T06:42:25Z |
| format | Journal Article |
| id | ntu-10356/99273 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T06:42:25Z |
| publishDate | 2014 |
| record_format | dspace |
| spelling | ntu-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. |
| 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 |
| 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_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_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_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 |
| topic | DRNTU::Science::Chemistry::Inorganic chemistry::Analysis |
| url | https://hdl.handle.net/10356/99273 http://hdl.handle.net/10220/19628 |
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