Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes

Autores
Salgado, Pablo; Contreras, David; Mansilla, Héctor D.; Márquez, Katherine; Vidal, Gladys; Cobos, Carlos Jorge; Martire, Daniel Osvaldo
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
This study reports on the kinetics of the early steps that mediate the reactions of substituted 1,2-dihydroxybenzenes (1,2-DHB) with Fe3+. The rate constants of the three processes identified by means of the stopped-flow technique are affected by the electron-withdrawing or electron-donating abilities of the substituent. The fastest process is assigned to the formation of a 1:1 complex between Fe3+ and the 1,2-DHB, which is accompanied by proton loss. The second process involves the inner-sphere electron transfer from the ligand to Fe3+ and the slowest step is related to the deprotonation of one of the oxygen atoms bonded to the metal. A reaction mechanism is proposed on the basis of the experimental data and density functional theory (DFT) calculations on mono- and bidentate species with different degrees of protonation.
Fil: Salgado, Pablo. Universidad de Concepción; Chile
Fil: Contreras, David. Universidad de Concepción; Chile
Fil: Mansilla, Héctor D.. Universidad de Concepción; Chile
Fil: Márquez, Katherine. Universidad de Concepción; Chile
Fil: Vidal, Gladys. Universidad de Concepción; Chile
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Martire, Daniel Osvaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
Siderophores
Iron(Iii)
Reduction
Stopped-Flow
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/63917
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenesSalgado, PabloContreras, DavidMansilla, Héctor D.Márquez, KatherineVidal, GladysCobos, Carlos JorgeMartire, Daniel OsvaldoSiderophoresIron(Iii)ReductionStopped-Flowhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1This study reports on the kinetics of the early steps that mediate the reactions of substituted 1,2-dihydroxybenzenes (1,2-DHB) with Fe3+. The rate constants of the three processes identified by means of the stopped-flow technique are affected by the electron-withdrawing or electron-donating abilities of the substituent. The fastest process is assigned to the formation of a 1:1 complex between Fe3+ and the 1,2-DHB, which is accompanied by proton loss. The second process involves the inner-sphere electron transfer from the ligand to Fe3+ and the slowest step is related to the deprotonation of one of the oxygen atoms bonded to the metal. A reaction mechanism is proposed on the basis of the experimental data and density functional theory (DFT) calculations on mono- and bidentate species with different degrees of protonation.Fil: Salgado, Pablo. Universidad de Concepción; ChileFil: Contreras, David. Universidad de Concepción; ChileFil: Mansilla, Héctor D.. Universidad de Concepción; ChileFil: Márquez, Katherine. Universidad de Concepción; ChileFil: Vidal, Gladys. Universidad de Concepción; ChileFil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Martire, Daniel Osvaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaRoyal Society of Chemistry2017-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/63917Salgado, Pablo; Contreras, David; Mansilla, Héctor D.; Márquez, Katherine; Vidal, Gladys; et al.; Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes; Royal Society of Chemistry; New Journal of Chemistry; 41; 21; 9-2017; 12685-126931144-0546CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/c7nj01322ainfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2017/NJ/C7NJ01322Ainfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:06:23Zoai:ri.conicet.gov.ar:11336/63917instacron: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:34982025-10-22 11:06:24.049CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes
title Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes
spellingShingle Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes
Salgado, Pablo
Siderophores
Iron(Iii)
Reduction
Stopped-Flow
title_short Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes
title_full Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes
title_fullStr Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes
title_full_unstemmed Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes
title_sort Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes
dc.creator.none.fl_str_mv Salgado, Pablo
Contreras, David
Mansilla, Héctor D.
Márquez, Katherine
Vidal, Gladys
Cobos, Carlos Jorge
Martire, Daniel Osvaldo
author Salgado, Pablo
author_facet Salgado, Pablo
Contreras, David
Mansilla, Héctor D.
Márquez, Katherine
Vidal, Gladys
Cobos, Carlos Jorge
Martire, Daniel Osvaldo
author_role author
author2 Contreras, David
Mansilla, Héctor D.
Márquez, Katherine
Vidal, Gladys
Cobos, Carlos Jorge
Martire, Daniel Osvaldo
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Siderophores
Iron(Iii)
Reduction
Stopped-Flow
topic Siderophores
Iron(Iii)
Reduction
Stopped-Flow
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv This study reports on the kinetics of the early steps that mediate the reactions of substituted 1,2-dihydroxybenzenes (1,2-DHB) with Fe3+. The rate constants of the three processes identified by means of the stopped-flow technique are affected by the electron-withdrawing or electron-donating abilities of the substituent. The fastest process is assigned to the formation of a 1:1 complex between Fe3+ and the 1,2-DHB, which is accompanied by proton loss. The second process involves the inner-sphere electron transfer from the ligand to Fe3+ and the slowest step is related to the deprotonation of one of the oxygen atoms bonded to the metal. A reaction mechanism is proposed on the basis of the experimental data and density functional theory (DFT) calculations on mono- and bidentate species with different degrees of protonation.
Fil: Salgado, Pablo. Universidad de Concepción; Chile
Fil: Contreras, David. Universidad de Concepción; Chile
Fil: Mansilla, Héctor D.. Universidad de Concepción; Chile
Fil: Márquez, Katherine. Universidad de Concepción; Chile
Fil: Vidal, Gladys. Universidad de Concepción; Chile
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Martire, Daniel Osvaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description This study reports on the kinetics of the early steps that mediate the reactions of substituted 1,2-dihydroxybenzenes (1,2-DHB) with Fe3+. The rate constants of the three processes identified by means of the stopped-flow technique are affected by the electron-withdrawing or electron-donating abilities of the substituent. The fastest process is assigned to the formation of a 1:1 complex between Fe3+ and the 1,2-DHB, which is accompanied by proton loss. The second process involves the inner-sphere electron transfer from the ligand to Fe3+ and the slowest step is related to the deprotonation of one of the oxygen atoms bonded to the metal. A reaction mechanism is proposed on the basis of the experimental data and density functional theory (DFT) calculations on mono- and bidentate species with different degrees of protonation.
publishDate 2017
dc.date.none.fl_str_mv 2017-09
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/11336/63917
Salgado, Pablo; Contreras, David; Mansilla, Héctor D.; Márquez, Katherine; Vidal, Gladys; et al.; Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes; Royal Society of Chemistry; New Journal of Chemistry; 41; 21; 9-2017; 12685-12693
1144-0546
CONICET Digital
CONICET
url http://hdl.handle.net/11336/63917
identifier_str_mv Salgado, Pablo; Contreras, David; Mansilla, Héctor D.; Márquez, Katherine; Vidal, Gladys; et al.; Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes; Royal Society of Chemistry; New Journal of Chemistry; 41; 21; 9-2017; 12685-12693
1144-0546
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/c7nj01322a
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2017/NJ/C7NJ01322A
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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
_version_ 1846781361408442368
score 12.982451

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