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Modulation of metal carbonyl stretching frequencies in the second coordination sphere through the internal Stark effect

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Parker, Gemma L., Van Lommel, R., Roig, N., Alonso, M. (Maria) and Chaplin, Adrian B. (2022) Modulation of metal carbonyl stretching frequencies in the second coordination sphere through the internal Stark effect. Chemistry - A European Journal . doi:10.1002/chem.202202283 ISSN 1521-3765. (In Press)

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Official URL: https://doi.org/10.1002/chem.202202283

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Abstract

Spectroscopic and computational examination of a homologous series of rhodium(I) pybox carbonyl complexes has revealed a correlation between the conformation of the flanking aryl-substituted oxazoline donors and the carbonyl stretching frequency. This relationship is also observed experimentally for octahedral rhodium(III) and ruthenium(II) variants and cannot be explained through the classical, Dewar–Chatt–Duncanson, interpretation of metal-carbonyl bonding. Instead, these findings are reconciled by local changes in the magnitude of the electric field that is projected along the metal-carbonyl vector: the internal Stark effect.

Item Type: Journal Article
Subjects: Q Science > QC Physics
Q Science > QD Chemistry
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH): Metal carbonyls , Electrostatics, Macrocyclic compounds, Rotaxanes , Organometallic chemistry
Journal or Publication Title: Chemistry - A European Journal
Publisher: Wiley-Blackwell Publishing Ltd.
ISSN: 1521-3765
Official Date: 2022
Dates:
DateEvent
2022Published
9 September 2022Available
9 September 2022Accepted
DOI: 10.1002/chem.202202283
Status: Peer Reviewed
Publication Status: In Press
Access rights to Published version: Open Access (Creative Commons)
Copyright Holders: © 2022 Wiley-VCH GmbH
Date of first compliant deposit: 9 September 2022
Date of first compliant Open Access: 14 October 2022
RIOXX Funder/Project Grant:
Project/Grant IDRIOXX Funder NameFunder ID
637313European Research Councilhttp://dx.doi.org/10.13039/501100000781
1185221NFonds voor Wetenschappelijk Onderzoek--Vlaanderenhttp://viaf.org/viaf/124392886
12F4416NFonds voor Wetenschappelijk Onderzoek--Vlaanderenhttp://viaf.org/viaf/124392886
UNSPECIFIEDEutopia FoundationUNSPECIFIED
UNSPECIFIEDVrije Universiteit Brusselhttp://dx.doi.org/10.13039/501100004418
UF100592Royal Societyhttp://dx.doi.org/10.13039/501100000288
UF150675Royal Societyhttp://dx.doi.org/10.13039/501100000288
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