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Zinc‐Promoted ZnMe/ZnPh Exchange in Eight‐Coordinate [Ru(PPh(3))(2)(ZnMe)(4)H(2)]
The syntheses, reactivity and electronic structure analyses of [Ru(PPh(3))(2)(ZnMe)(4)H(2)], 1 a, and [Ru(PPh(3))(2)(ZnPh)(4)H(2)], 2 b, are reported. 1 a exhibits an 8‐coordinate Ru centre with axial phosphines and a symmetrical (2 : 2) arrangement of ZnMe ligands in the equatorial plane. The ZnMe...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9311408/ https://www.ncbi.nlm.nih.gov/pubmed/35213937 http://dx.doi.org/10.1002/anie.202117495 |
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author | Sotorrios, Lia Miloserdov, Fedor M. Pécharman, Anne‐Frédérique Lowe, John P. Macgregor, Stuart A. Mahon, Mary F. Whittlesey, Michael K. |
author_facet | Sotorrios, Lia Miloserdov, Fedor M. Pécharman, Anne‐Frédérique Lowe, John P. Macgregor, Stuart A. Mahon, Mary F. Whittlesey, Michael K. |
author_sort | Sotorrios, Lia |
collection | PubMed |
description | The syntheses, reactivity and electronic structure analyses of [Ru(PPh(3))(2)(ZnMe)(4)H(2)], 1 a, and [Ru(PPh(3))(2)(ZnPh)(4)H(2)], 2 b, are reported. 1 a exhibits an 8‐coordinate Ru centre with axial phosphines and a symmetrical (2 : 2) arrangement of ZnMe ligands in the equatorial plane. The ZnMe ligands in 1 a undergo facile, sequential exchange with ZnPh(2) to give 2 b, which shows a 3 : 1 arrangement of ZnPh ligands. Both 1 a and 2 b exist in equilibrium with their respective 3 : 1 and 2 : 2 isomers. Mechanisms for ZnMe/ZnPh exchange and isomerisation are proposed using DFT calculations. The relationships of these {Ru(ZnR)(4)H(2)} species to isoelectronic Group 8 transition metal polyhydrides and related Schlenk equilibria in the Negishi reaction are discussed. |
format | Online Article Text |
id | pubmed-9311408 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-93114082022-07-29 Zinc‐Promoted ZnMe/ZnPh Exchange in Eight‐Coordinate [Ru(PPh(3))(2)(ZnMe)(4)H(2)] Sotorrios, Lia Miloserdov, Fedor M. Pécharman, Anne‐Frédérique Lowe, John P. Macgregor, Stuart A. Mahon, Mary F. Whittlesey, Michael K. Angew Chem Int Ed Engl Communications The syntheses, reactivity and electronic structure analyses of [Ru(PPh(3))(2)(ZnMe)(4)H(2)], 1 a, and [Ru(PPh(3))(2)(ZnPh)(4)H(2)], 2 b, are reported. 1 a exhibits an 8‐coordinate Ru centre with axial phosphines and a symmetrical (2 : 2) arrangement of ZnMe ligands in the equatorial plane. The ZnMe ligands in 1 a undergo facile, sequential exchange with ZnPh(2) to give 2 b, which shows a 3 : 1 arrangement of ZnPh ligands. Both 1 a and 2 b exist in equilibrium with their respective 3 : 1 and 2 : 2 isomers. Mechanisms for ZnMe/ZnPh exchange and isomerisation are proposed using DFT calculations. The relationships of these {Ru(ZnR)(4)H(2)} species to isoelectronic Group 8 transition metal polyhydrides and related Schlenk equilibria in the Negishi reaction are discussed. John Wiley and Sons Inc. 2022-03-14 2022-05-02 /pmc/articles/PMC9311408/ /pubmed/35213937 http://dx.doi.org/10.1002/anie.202117495 Text en © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Communications Sotorrios, Lia Miloserdov, Fedor M. Pécharman, Anne‐Frédérique Lowe, John P. Macgregor, Stuart A. Mahon, Mary F. Whittlesey, Michael K. Zinc‐Promoted ZnMe/ZnPh Exchange in Eight‐Coordinate [Ru(PPh(3))(2)(ZnMe)(4)H(2)] |
title | Zinc‐Promoted ZnMe/ZnPh Exchange in Eight‐Coordinate [Ru(PPh(3))(2)(ZnMe)(4)H(2)] |
title_full | Zinc‐Promoted ZnMe/ZnPh Exchange in Eight‐Coordinate [Ru(PPh(3))(2)(ZnMe)(4)H(2)] |
title_fullStr | Zinc‐Promoted ZnMe/ZnPh Exchange in Eight‐Coordinate [Ru(PPh(3))(2)(ZnMe)(4)H(2)] |
title_full_unstemmed | Zinc‐Promoted ZnMe/ZnPh Exchange in Eight‐Coordinate [Ru(PPh(3))(2)(ZnMe)(4)H(2)] |
title_short | Zinc‐Promoted ZnMe/ZnPh Exchange in Eight‐Coordinate [Ru(PPh(3))(2)(ZnMe)(4)H(2)] |
title_sort | zinc‐promoted znme/znph exchange in eight‐coordinate [ru(pph(3))(2)(znme)(4)h(2)] |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9311408/ https://www.ncbi.nlm.nih.gov/pubmed/35213937 http://dx.doi.org/10.1002/anie.202117495 |
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