Generation of a π-Bonded Isomer of [P4]4− by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3
By employing the highly reducing aluminyl complex [K{(NON)Al}]<sub>2</sub> (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene), we demonstrate the controlled formation of P<sub>4</sub> <sup>2-</sup&...
| Main Authors: | , , , |
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| Format: | Journal article |
| Language: | English |
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Wiley
2021
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| _version_ | 1826289037665632256 |
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| author | Roy, MMD Heilmann, A Ellwanger, MA Aldridge, S |
| author_facet | Roy, MMD Heilmann, A Ellwanger, MA Aldridge, S |
| author_sort | Roy, MMD |
| collection | OXFORD |
| description | By employing the highly reducing aluminyl complex [K{(NON)Al}]<sub>2</sub> (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene), we demonstrate the controlled formation of P<sub>4</sub> <sup>2-</sup> and P<sub>4</sub> <sup>4-</sup> complexes from white phosphorus, and chemically reversible inter-conversion between them. The tetra-anion features a unique planar π-bonded structure, with the incorporation of the K<sup>+</sup> cations implicit in the use of the anionic nucleophile offering additional stabilization of the unsaturated isomer of the P<sub>4</sub> <sup>4-</sup> fragment. This complex is extremely reactive, acting as a source of P<sup>3-</sup> : exposure to ammonia leads to the release of phosphine (PH<sub>3</sub> ) under mild conditions (room temperature and pressure), which contrast with those necessitated for the direct combination of P<sub>4</sub> and NH<sub>3</sub> (>5 kbar and >250 °C). |
| first_indexed | 2024-03-07T02:22:48Z |
| format | Journal article |
| id | oxford-uuid:a48921bb-0ae7-4c11-a74f-be05627aa62a |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T02:22:48Z |
| publishDate | 2021 |
| publisher | Wiley |
| record_format | dspace |
| spelling | oxford-uuid:a48921bb-0ae7-4c11-a74f-be05627aa62a2022-03-27T02:34:26ZGeneration of a π-Bonded Isomer of [P4]4− by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:a48921bb-0ae7-4c11-a74f-be05627aa62aEnglishSymplectic ElementsWiley2021Roy, MMDHeilmann, AEllwanger, MAAldridge, SBy employing the highly reducing aluminyl complex [K{(NON)Al}]<sub>2</sub> (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene), we demonstrate the controlled formation of P<sub>4</sub> <sup>2-</sup> and P<sub>4</sub> <sup>4-</sup> complexes from white phosphorus, and chemically reversible inter-conversion between them. The tetra-anion features a unique planar π-bonded structure, with the incorporation of the K<sup>+</sup> cations implicit in the use of the anionic nucleophile offering additional stabilization of the unsaturated isomer of the P<sub>4</sub> <sup>4-</sup> fragment. This complex is extremely reactive, acting as a source of P<sup>3-</sup> : exposure to ammonia leads to the release of phosphine (PH<sub>3</sub> ) under mild conditions (room temperature and pressure), which contrast with those necessitated for the direct combination of P<sub>4</sub> and NH<sub>3</sub> (>5 kbar and >250 °C). |
| spellingShingle | Roy, MMD Heilmann, A Ellwanger, MA Aldridge, S Generation of a π-Bonded Isomer of [P4]4− by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3 |
| title | Generation of a π-Bonded Isomer of [P4]4− by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3 |
| title_full | Generation of a π-Bonded Isomer of [P4]4− by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3 |
| title_fullStr | Generation of a π-Bonded Isomer of [P4]4− by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3 |
| title_full_unstemmed | Generation of a π-Bonded Isomer of [P4]4− by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3 |
| title_short | Generation of a π-Bonded Isomer of [P4]4− by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3 |
| title_sort | generation of a π bonded isomer of p4 4 by aluminyl reduction of white phosphorus and its ammonolysis to ph3 |
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