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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...

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Autores principales: Sotorrios, Lia, Miloserdov, Fedor M., Pécharman, Anne‐Frédérique, Lowe, John P., Macgregor, Stuart A., Mahon, Mary F., Whittlesey, Michael K.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
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.
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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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