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

Lia Sotorrios; Fedor M. Miloserdov; Anne Frédérique Pécharman; John P. Lowe; Stuart A. Macgregor; Mary F. Mahon; Michael K. Whittlesey

doi:10.1002/anie.202117495

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

Lia Sotorrios, Fedor M. Miloserdov^*, Anne Frédérique Pécharman, John P. Lowe, Stuart A. Macgregor^*, Mary F. Mahon, Michael K. Whittlesey^*

^*Corresponding author for this work

School of Chemistry

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

Abstract

The syntheses, reactivity and electronic structure analyses of [Ru(PPh₃)₂(ZnMe)₄H₂], 1 a, and [Ru(PPh₃)₂(ZnPh)₄H₂], 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 ZnPh₂ 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)₄H₂} 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

Keywords

Density Functional Calculations
Heterometallic Complexes
Hydrides
Ruthenium
Zinc

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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(PPh3)2(ZnMe)4H2], 1 a, and [Ru(PPh3)2(ZnPh)4H2], 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 ZnPh2 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)4H2} 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 Miloserdov, {Fedor M.} and P{\'e}charman, {Anne Fr{\'e}d{\'e}rique} and Lowe, {John P.} and Macgregor, {Stuart A.} and Mahon, {Mary F.} and Whittlesey, {Michael K.}",

note = "Publisher Copyright: {\textcopyright} 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2022",

month = may,

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doi = "10.1002/anie.202117495",

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T1 - Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh3)2(ZnMe)4H2]

AU - Sotorrios, Lia

AU - Miloserdov, Fedor M.

AU - Pécharman, Anne Frédérique

AU - Lowe, John P.

AU - Macgregor, Stuart A.

AU - Mahon, Mary F.

AU - Whittlesey, Michael K.

PY - 2022/5/2

Y1 - 2022/5/2

N2 - The syntheses, reactivity and electronic structure analyses of [Ru(PPh3)2(ZnMe)4H2], 1 a, and [Ru(PPh3)2(ZnPh)4H2], 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 ZnPh2 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)4H2} 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(PPh3)2(ZnMe)4H2], 1 a, and [Ru(PPh3)2(ZnPh)4H2], 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 ZnPh2 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)4H2} 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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SN - 1433-7851

VL - 61

JO - Angewandte Chemie - International Edition

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M1 - e202117495

ER -

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

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