Acid–Responsive Rhenium(I) NHC Complexes: Pyrazine vs Pyridine

Four rhenium(I) tricarbonyl complexes featuring pyridine- or pyrazine-functionalized N-heterocyclic carbenes were synthesized and fully characterized, including the determination of their molecular structures by single-crystal X-ray diffraction. Electrochemical and spectroelectrochemical measurement...

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Detalles Bibliográficos
Autores: Abate, Pedro O., Rizo, Juan Francisco, Fernández de Córdova, Francisco J., Ros, Abel, Rivada-Wheelaghan, Orestes
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2026
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/419763
Acceso en línea:http://hdl.handle.net/10261/419763
Access Level:acceso abierto
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spelling Acid–Responsive Rhenium(I) NHC Complexes: Pyrazine vs PyridineAbate, Pedro O.Rizo, Juan FranciscoFernández de Córdova, Francisco J.Ros, AbelRivada-Wheelaghan, OrestesFour rhenium(I) tricarbonyl complexes featuring pyridine- or pyrazine-functionalized N-heterocyclic carbenes were synthesized and fully characterized, including the determination of their molecular structures by single-crystal X-ray diffraction. Electrochemical and spectroelectrochemical measurements were performed. The development of isosteric Re(I) complexes enabled a direct comparison of how Brønsted and Lewis acids influence their electronic properties. Complexes containing the pyridyl core showed no detectable changes in either electrochemical or spectroscopic studies. In contrast, those bearing the pyrazine fragment exhibited significant shifts at both reductive and oxidative potentials, attributable to the extra nitrogen atom in the 1,4-diazine ring, which can interact with Brønsted (and Lewis) acids. In this regard, comparison of alkali salts with Brønsted acids revealed that the presence of the latter induces substantially larger electronic perturbationsThe authors greatly acknowledge the financial support through the grants CNS2022-135765, RED2018-102387-T, RYC2020-028851-I funded by MCIN/AEI/10.13039/501100011033; the Junta de Andalucía through the grant PROYEXCEL_00746; and the financial support received from the Universidad de Sevilla through the program TALENTO. The use of computational facilities of the Super-computing Centre of Galicia (CESGA) is gratefully acknowledged. We thank Dr. Noa Burshtein for scientific editing of the manuscript.Peer reviewedRoyal Society of Chemistry (UK)Ministerio de Ciencia e Innovación (España)Agencia Estatal de Investigación (España)Junta de AndalucíaUniversidad de Sevilla0000-0002-3455-56750000-0003-0381-59370009-0008-3238-33560000-0002-1784-2840Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202620262026info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/419763reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI//RYC2020-028851-Iinfo:eu-repo/grantAgreement/AEI//CNS2022-135765info:eu-repo/grantAgreement/AEI//RED2018-102387-TThe underlying dataset has been published as supplementary material of the article in the publisher platform at DOI https://doi.org/10.1039/D6DT00158Khttps://doi.org/10.1039/D6DT00158KSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/4197632026-05-22T06:33:51Z
dc.title.none.fl_str_mv Acid–Responsive Rhenium(I) NHC Complexes: Pyrazine vs Pyridine
title Acid–Responsive Rhenium(I) NHC Complexes: Pyrazine vs Pyridine
spellingShingle Acid–Responsive Rhenium(I) NHC Complexes: Pyrazine vs Pyridine
Abate, Pedro O.
title_short Acid–Responsive Rhenium(I) NHC Complexes: Pyrazine vs Pyridine
title_full Acid–Responsive Rhenium(I) NHC Complexes: Pyrazine vs Pyridine
title_fullStr Acid–Responsive Rhenium(I) NHC Complexes: Pyrazine vs Pyridine
title_full_unstemmed Acid–Responsive Rhenium(I) NHC Complexes: Pyrazine vs Pyridine
title_sort Acid–Responsive Rhenium(I) NHC Complexes: Pyrazine vs Pyridine
dc.creator.none.fl_str_mv Abate, Pedro O.
Rizo, Juan Francisco
Fernández de Córdova, Francisco J.
Ros, Abel
Rivada-Wheelaghan, Orestes
author Abate, Pedro O.
author_facet Abate, Pedro O.
Rizo, Juan Francisco
Fernández de Córdova, Francisco J.
Ros, Abel
Rivada-Wheelaghan, Orestes
author_role author
author2 Rizo, Juan Francisco
Fernández de Córdova, Francisco J.
Ros, Abel
Rivada-Wheelaghan, Orestes
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
Agencia Estatal de Investigación (España)
Junta de Andalucía
Universidad de Sevilla
0000-0002-3455-5675
0000-0003-0381-5937
0009-0008-3238-3356
0000-0002-1784-2840
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Four rhenium(I) tricarbonyl complexes featuring pyridine- or pyrazine-functionalized N-heterocyclic carbenes were synthesized and fully characterized, including the determination of their molecular structures by single-crystal X-ray diffraction. Electrochemical and spectroelectrochemical measurements were performed. The development of isosteric Re(I) complexes enabled a direct comparison of how Brønsted and Lewis acids influence their electronic properties. Complexes containing the pyridyl core showed no detectable changes in either electrochemical or spectroscopic studies. In contrast, those bearing the pyrazine fragment exhibited significant shifts at both reductive and oxidative potentials, attributable to the extra nitrogen atom in the 1,4-diazine ring, which can interact with Brønsted (and Lewis) acids. In this regard, comparison of alkali salts with Brønsted acids revealed that the presence of the latter induces substantially larger electronic perturbations
publishDate 2026
dc.date.none.fl_str_mv 2026
2026
2026
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/419763
url http://hdl.handle.net/10261/419763
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI//RYC2020-028851-I
info:eu-repo/grantAgreement/AEI//CNS2022-135765
info:eu-repo/grantAgreement/AEI//RED2018-102387-T
The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI https://doi.org/10.1039/D6DT00158K
https://doi.org/10.1039/D6DT00158K
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry (UK)
publisher.none.fl_str_mv Royal Society of Chemistry (UK)
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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