Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh3)2(ZnMe)4H2]

Lia Sotorrios; Fedor Miloserdov; Anne-Frédérique Pecharman; John Lowe; Stuart Macgregor; Mary Mahon; Michael Whittlesey

doi:10.1002/anie.202117495

Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh₃)₂(ZnMe)₄H₂]

Lia Sotorrios, Fedor Miloserdov, Anne-Frédérique Pecharman, John Lowe, Stuart Macgregor, Mary Mahon, Michael Whittlesey

Research output: Contribution to journal › Article › peer-review

5 Citations (SciVal)

Abstract

The syntheses, reactivity and electronic structure analyses of [Ru(PPh 3 ) 2 (ZnMe) 4 H 2 ], 1a , and [Ru(PPh 3 ) 2 (ZnPh) 4 H 2 ], 2b , are reported. 1a 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 1a undergo facile, sequential exchange with ZnPh 2 to give 2b , which shows a 3:1 arrangement of ZnPh ligands. Both 1a and 2b 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.

Original language	English
Article number	e202117495
Journal	Angewandte Chemie International Edition
Volume	61
Issue number	19
Early online date	14 Mar 2022
DOIs	https://doi.org/10.1002/anie.202117495
Publication status	Published - 2 May 2022

Bibliographical note

Funding Information:
We thank the EU's Horizon 2020 research and innovation programme under Marie Skłodowska‐Curie grant agreement No 792674 (to FM) and EPSRC (grants EP/T019876/1 and EP/T019743/1) for funding.

Keywords

Density Functional Calculations
Heterometallic Complexes
Hydrides
Ruthenium
Zinc

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.202117495Licence: CC BY

Cite this

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title = "Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh3)2(ZnMe)4H2]",

abstract = "The syntheses, reactivity and electronic structure analyses of [Ru(PPh 3 ) 2 (ZnMe) 4 H 2 ], 1a , and [Ru(PPh 3 ) 2 (ZnPh) 4 H 2 ], 2b , are reported. 1a 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 1a undergo facile, sequential exchange with ZnPh 2 to give 2b , which shows a 3:1 arrangement of ZnPh ligands. Both 1a and 2b 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.",

keywords = "Density Functional Calculations, Heterometallic Complexes, Hydrides, Ruthenium, Zinc",

author = "Lia Sotorrios and Fedor Miloserdov and Anne-Fr{\'e}d{\'e}rique Pecharman and John Lowe and Stuart Macgregor and Mary Mahon and Michael Whittlesey",

note = "Funding Information: We thank the EU's Horizon 2020 research and innovation programme under Marie Sk{\l}odowska‐Curie grant agreement No 792674 (to FM) and EPSRC (grants EP/T019876/1 and EP/T019743/1) for funding. ",

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journal = "Angewandte Chemie International Edition",

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AU - Sotorrios, Lia

AU - Miloserdov, Fedor

AU - Pecharman, Anne-Frédérique

AU - Lowe, John

AU - Macgregor, Stuart

AU - Mahon, Mary

AU - Whittlesey, Michael

N1 - Funding Information: We thank the EU's Horizon 2020 research and innovation programme under Marie Skłodowska‐Curie grant agreement No 792674 (to FM) and EPSRC (grants EP/T019876/1 and EP/T019743/1) for funding.

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Y1 - 2022/5/2

N2 - The syntheses, reactivity and electronic structure analyses of [Ru(PPh 3 ) 2 (ZnMe) 4 H 2 ], 1a , and [Ru(PPh 3 ) 2 (ZnPh) 4 H 2 ], 2b , are reported. 1a 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 1a undergo facile, sequential exchange with ZnPh 2 to give 2b , which shows a 3:1 arrangement of ZnPh ligands. Both 1a and 2b 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.

AB - The syntheses, reactivity and electronic structure analyses of [Ru(PPh 3 ) 2 (ZnMe) 4 H 2 ], 1a , and [Ru(PPh 3 ) 2 (ZnPh) 4 H 2 ], 2b , are reported. 1a 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 1a undergo facile, sequential exchange with ZnPh 2 to give 2b , which shows a 3:1 arrangement of ZnPh ligands. Both 1a and 2b 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.

KW - Density Functional Calculations

KW - Heterometallic Complexes

KW - Hydrides

KW - Ruthenium

KW - Zinc

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ER -

Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh₃)₂(ZnMe)₄H₂]

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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Dual Unsaturated TM-M' Heterobimetallic Complexes for Cooperative Activation and Catalysis

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Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh3)2(ZnMe)4H2]

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

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Dual Unsaturated TM-M' Heterobimetallic Complexes for Cooperative Activation and Catalysis

Cite this

Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh₃)₂(ZnMe)₄H₂]