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Stereoisomerism of bis(sigma-Zincane) complexes: evidence for an intramolecular pathway

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Title: Stereoisomerism of bis(sigma-Zincane) complexes: evidence for an intramolecular pathway
Authors: Ekkert, O
White, AJP
Crimmin, MR
Item Type: Journal Article
Abstract: The first bis(σ-zincane) complexes, heterotri- metallic species [M(CO)4(η2-HZnBDI)2], have been prepared (BDI=κ2-{2,6-(iPr)2C6H3NCMe}2CH). For M=Cr, a single stereoisomer is observed in solution and the solid-state. For M=Mo and W, cis and trans isomers were found to reversibly interconvert at 297 K. Despite the huge steric demands of the ligand on zinc, the cis isomer was found to be the most thermodynamically stable in all cases. The activation parameters for the isomerisation when M=Mo are ΔH≠=20.8 kcal mol−1 and ΔS≠=−12.8 cal K−1 mol−1. In combination with DFT calculations, the negative activation entropy suggests an intramolecular rotation mechanism for isomerisation.
Issue Date: 5-Apr-2017
Date of Acceptance: 23-Mar-2017
URI: http://hdl.handle.net/10044/1/48429
DOI: https://dx.doi.org/10.1002/chem.201701207
ISSN: 1521-3765
Publisher: Wiley
Start Page: 5682
End Page: 5686
Journal / Book Title: Chemistry-A European Journal
Volume: 23
Issue: 24
Copyright Statement: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Sponsor/Funder: The Royal Society
Commission of the European Communities
Funder's Grant Number: UF090149
655474
Keywords: Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
isomerisation
mechanism
reaction pathways
zinc hydride
sigma-complexes
TRANSITION-METAL CENTERS
X-RAY-STRUCTURE
RUTHENIUM COMPLEXES
DIHYDROGEN COMPLEXES
SIGMA-COMPLEXES
SPECTROSCOPIC EVIDENCE
SECONDARY INTERACTIONS
CARBONYL-COMPLEXES
HYDROGEN BOND
H BONDS
σ-complexes
General Chemistry
03 Chemical Sciences
Publication Status: Published
Appears in Collections:Chemistry
Faculty of Natural Sciences



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