Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes

Autores
Castaño Castañeda, Laura Cristina; Angelillo, Bruno; Mercado, Brandon Q.; Di Salvo, Florencia; Cattaneo, Mauricio
Año de publicación
2026
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Extensive studies on the dehydrogenative oxidation of alkylamines on transition metals represent a generalized reactivity, with some reports on accessible intermediates and reactive species offering different interpretations. Here, the electrochemical oxidation of ruthenium amine complexes is examined to evaluate the reactivity of high-valent species. We report a combined spectroelectrochemical and DFT study of the complexes [RuII(bpy)2(LL)]2+ with LL = (NH3)2, en (ethylenediamine), and en* (2,3-dimethyl-2,3-diamino-butane), and bpy = 2,2′-bipyridine. Comparison among these three complexes revealed different electrochemical oxidation mechanistic pathways, yet all of them follow the same overall acid–base–dependent reactivity. In both protic and aprotic solvents, the first oxidation proceeds as a pure one-electron process under strongly acidic conditions. In the presence of a base, a multiproton-coupled electron transfer (PCET) process completes the net 2e–/2H+ reaction. The oxidation mechanism of [Ru(bpy)2(en*)]2+ is revisited to achieve improved consistency with long-standing experimental proposals. Electrochemical and spectral analysis, along with DFT calculations, support the assignment of the intermediates formed. Molecular orbital analysis reveals interactions between dπRu and pNsp2 orbitals, which stabilize specific reaction intermediates through geometric constraints. This report highlights the relevance of Ru-amine/amido complexes as multi-PCET redox models for bond-activation catalysis.
Fil: Castaño Castañeda, Laura Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Angelillo, Bruno. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Mercado, Brandon Q.. University of Yale; Estados Unidos
Fil: Di Salvo, Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Cattaneo, Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Materia
Ruthenium complexes
Multiredox
Amine oxidative dehydrogenation
High-valent intermediates
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/286222
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium ComplexesCastaño Castañeda, Laura CristinaAngelillo, BrunoMercado, Brandon Q.Di Salvo, FlorenciaCattaneo, MauricioRuthenium complexesMultiredoxAmine oxidative dehydrogenationHigh-valent intermediateshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Extensive studies on the dehydrogenative oxidation of alkylamines on transition metals represent a generalized reactivity, with some reports on accessible intermediates and reactive species offering different interpretations. Here, the electrochemical oxidation of ruthenium amine complexes is examined to evaluate the reactivity of high-valent species. We report a combined spectroelectrochemical and DFT study of the complexes [RuII(bpy)2(LL)]2+ with LL = (NH3)2, en (ethylenediamine), and en* (2,3-dimethyl-2,3-diamino-butane), and bpy = 2,2′-bipyridine. Comparison among these three complexes revealed different electrochemical oxidation mechanistic pathways, yet all of them follow the same overall acid–base–dependent reactivity. In both protic and aprotic solvents, the first oxidation proceeds as a pure one-electron process under strongly acidic conditions. In the presence of a base, a multiproton-coupled electron transfer (PCET) process completes the net 2e–/2H+ reaction. The oxidation mechanism of [Ru(bpy)2(en*)]2+ is revisited to achieve improved consistency with long-standing experimental proposals. Electrochemical and spectral analysis, along with DFT calculations, support the assignment of the intermediates formed. Molecular orbital analysis reveals interactions between dπRu and pNsp2 orbitals, which stabilize specific reaction intermediates through geometric constraints. This report highlights the relevance of Ru-amine/amido complexes as multi-PCET redox models for bond-activation catalysis.Fil: Castaño Castañeda, Laura Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Angelillo, Bruno. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Mercado, Brandon Q.. University of Yale; Estados UnidosFil: Di Salvo, Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Cattaneo, Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaAmerican Chemical Society2026-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/286222Castaño Castañeda, Laura Cristina; Angelillo, Bruno; Mercado, Brandon Q.; Di Salvo, Florencia; Cattaneo, Mauricio; Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes; American Chemical Society; ACS Omega; 11; 11; 3-2026; 1-162470-13432470-1343CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acsomega.5c12371info:eu-repo/semantics/altIdentifier/doi/10.1021/acsomega.5c12371info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-08-25T14:33:08Zoai:ri.conicet.gov.ar:11336/286222instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982026-08-25 14:33:09.499CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes
title Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes
spellingShingle Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes
Castaño Castañeda, Laura Cristina
Ruthenium complexes
Multiredox
Amine oxidative dehydrogenation
High-valent intermediates
title_short Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes
title_full Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes
title_fullStr Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes
title_full_unstemmed Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes
title_sort Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes
dc.creator.none.fl_str_mv Castaño Castañeda, Laura Cristina
Angelillo, Bruno
Mercado, Brandon Q.
Di Salvo, Florencia
Cattaneo, Mauricio
author Castaño Castañeda, Laura Cristina
author_facet Castaño Castañeda, Laura Cristina
Angelillo, Bruno
Mercado, Brandon Q.
Di Salvo, Florencia
Cattaneo, Mauricio
author_role author
author2 Angelillo, Bruno
Mercado, Brandon Q.
Di Salvo, Florencia
Cattaneo, Mauricio
author2_role author
author
author
author
dc.subject.none.fl_str_mv Ruthenium complexes
Multiredox
Amine oxidative dehydrogenation
High-valent intermediates
topic Ruthenium complexes
Multiredox
Amine oxidative dehydrogenation
High-valent intermediates
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Extensive studies on the dehydrogenative oxidation of alkylamines on transition metals represent a generalized reactivity, with some reports on accessible intermediates and reactive species offering different interpretations. Here, the electrochemical oxidation of ruthenium amine complexes is examined to evaluate the reactivity of high-valent species. We report a combined spectroelectrochemical and DFT study of the complexes [RuII(bpy)2(LL)]2+ with LL = (NH3)2, en (ethylenediamine), and en* (2,3-dimethyl-2,3-diamino-butane), and bpy = 2,2′-bipyridine. Comparison among these three complexes revealed different electrochemical oxidation mechanistic pathways, yet all of them follow the same overall acid–base–dependent reactivity. In both protic and aprotic solvents, the first oxidation proceeds as a pure one-electron process under strongly acidic conditions. In the presence of a base, a multiproton-coupled electron transfer (PCET) process completes the net 2e–/2H+ reaction. The oxidation mechanism of [Ru(bpy)2(en*)]2+ is revisited to achieve improved consistency with long-standing experimental proposals. Electrochemical and spectral analysis, along with DFT calculations, support the assignment of the intermediates formed. Molecular orbital analysis reveals interactions between dπRu and pNsp2 orbitals, which stabilize specific reaction intermediates through geometric constraints. This report highlights the relevance of Ru-amine/amido complexes as multi-PCET redox models for bond-activation catalysis.
Fil: Castaño Castañeda, Laura Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Angelillo, Bruno. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Mercado, Brandon Q.. University of Yale; Estados Unidos
Fil: Di Salvo, Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Cattaneo, Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
description Extensive studies on the dehydrogenative oxidation of alkylamines on transition metals represent a generalized reactivity, with some reports on accessible intermediates and reactive species offering different interpretations. Here, the electrochemical oxidation of ruthenium amine complexes is examined to evaluate the reactivity of high-valent species. We report a combined spectroelectrochemical and DFT study of the complexes [RuII(bpy)2(LL)]2+ with LL = (NH3)2, en (ethylenediamine), and en* (2,3-dimethyl-2,3-diamino-butane), and bpy = 2,2′-bipyridine. Comparison among these three complexes revealed different electrochemical oxidation mechanistic pathways, yet all of them follow the same overall acid–base–dependent reactivity. In both protic and aprotic solvents, the first oxidation proceeds as a pure one-electron process under strongly acidic conditions. In the presence of a base, a multiproton-coupled electron transfer (PCET) process completes the net 2e–/2H+ reaction. The oxidation mechanism of [Ru(bpy)2(en*)]2+ is revisited to achieve improved consistency with long-standing experimental proposals. Electrochemical and spectral analysis, along with DFT calculations, support the assignment of the intermediates formed. Molecular orbital analysis reveals interactions between dπRu and pNsp2 orbitals, which stabilize specific reaction intermediates through geometric constraints. This report highlights the relevance of Ru-amine/amido complexes as multi-PCET redox models for bond-activation catalysis.
publishDate 2026
dc.date.none.fl_str_mv 2026-03
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/286222
Castaño Castañeda, Laura Cristina; Angelillo, Bruno; Mercado, Brandon Q.; Di Salvo, Florencia; Cattaneo, Mauricio; Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes; American Chemical Society; ACS Omega; 11; 11; 3-2026; 1-16
2470-1343
2470-1343
CONICET Digital
CONICET
url http://hdl.handle.net/11336/286222
identifier_str_mv Castaño Castañeda, Laura Cristina; Angelillo, Bruno; Mercado, Brandon Q.; Di Salvo, Florencia; Cattaneo, Mauricio; Molecular Constraints and Electronic Structure Direct Multi-Step PCET Mechanisms in the Electrochemical Oxidation of Ruthenium Complexes; American Chemical Society; ACS Omega; 11; 11; 3-2026; 1-16
2470-1343
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acsomega.5c12371
info:eu-repo/semantics/altIdentifier/doi/10.1021/acsomega.5c12371
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.265058

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