The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms

Autores
Yerien, Damián Emilio; Barata Vallejo, Sebastian; Mora Flores, Erwin Wilfredo; Postigo, Jose Alberto
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Photoinitiated perfluorobutylation reactions of 2-anisidine 1, propenyloxybenzene 2, and 2-mercaptoethanol 3 have been carried out employing commercially available n-C4F9I as the source of C4F9 radicals under three different photocatalysts (PCs) absorbing in the violet (Ir[dF(CF3)ppy]2(dtbbpy)+ (PC-1)), green (Rose Bengal (PC-2)) and red (zinc phthalocyanine PhZn (PC-3)) regions of the electromagnetic spectrum, in order to explore the quantum yields and radical chain lengths for each type of transformation and photoinitiated system. For substrates 1-3 and their different types of reactions, the comparative study between PCs seeks to establish the extent to which regioproducts, yields, and mechanistic proposals are influenced by the intervention of each PC. The different overall quantum yields and chain lengths obtained for each type of reaction under each PC are a direct consequence of the efficiency of the photoinitiation events, i.e., primary radical production, propagation and termination steps. This will have important implications in the understanding and representations of the mechanisms postulated, in terms of closed and open catalytic cycles. One strategy we apply to uncover radical propagating chains in our mechanisms is to explore photocatalysts that operate in oxidative and reductive quenching manners for each type of transformation.
Fil: Yerien, Damián Emilio. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina
Fil: Barata Vallejo, Sebastian. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Centre National de la Recherche Scientifique; Francia
Fil: Mora Flores, Erwin Wilfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina
Fil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina
Materia
PHOTOCATALYSIS
RADICAL CHAIN
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:11336/135011
Acceder
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network_name_str CONICET Digital (CONICET)
spelling The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution MechanismsYerien, Damián EmilioBarata Vallejo, SebastianMora Flores, Erwin WilfredoPostigo, Jose AlbertoPHOTOCATALYSISRADICAL CHAINhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Photoinitiated perfluorobutylation reactions of 2-anisidine 1, propenyloxybenzene 2, and 2-mercaptoethanol 3 have been carried out employing commercially available n-C4F9I as the source of C4F9 radicals under three different photocatalysts (PCs) absorbing in the violet (Ir[dF(CF3)ppy]2(dtbbpy)+ (PC-1)), green (Rose Bengal (PC-2)) and red (zinc phthalocyanine PhZn (PC-3)) regions of the electromagnetic spectrum, in order to explore the quantum yields and radical chain lengths for each type of transformation and photoinitiated system. For substrates 1-3 and their different types of reactions, the comparative study between PCs seeks to establish the extent to which regioproducts, yields, and mechanistic proposals are influenced by the intervention of each PC. The different overall quantum yields and chain lengths obtained for each type of reaction under each PC are a direct consequence of the efficiency of the photoinitiation events, i.e., primary radical production, propagation and termination steps. This will have important implications in the understanding and representations of the mechanisms postulated, in terms of closed and open catalytic cycles. One strategy we apply to uncover radical propagating chains in our mechanisms is to explore photocatalysts that operate in oxidative and reductive quenching manners for each type of transformation.Fil: Yerien, Damián Emilio. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; ArgentinaFil: Barata Vallejo, Sebastian. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Centre National de la Recherche Scientifique; FranciaFil: Mora Flores, Erwin Wilfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; ArgentinaFil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; ArgentinaRoyal Society of Chemistry2020-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/135011Yerien, Damián Emilio; Barata Vallejo, Sebastian; Mora Flores, Erwin Wilfredo; Postigo, Jose Alberto; The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms; Royal Society of Chemistry; Catalysis Science & Technology; 10; 15; 8-2020; 5113-51282044-47612044-4761CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2020/CY/D0CY00921Kinfo:eu-repo/semantics/altIdentifier/doi/10.1039/D0CY00921Kinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:31:29Zoai:ri.conicet.gov.ar:11336/135011instacron: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:34982025-09-29 10:31:29.554CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms
title The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms
spellingShingle The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms
Yerien, Damián Emilio
PHOTOCATALYSIS
RADICAL CHAIN
title_short The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms
title_full The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms
title_fullStr The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms
title_full_unstemmed The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms
title_sort The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms
dc.creator.none.fl_str_mv Yerien, Damián Emilio
Barata Vallejo, Sebastian
Mora Flores, Erwin Wilfredo
Postigo, Jose Alberto
author Yerien, Damián Emilio
author_facet Yerien, Damián Emilio
Barata Vallejo, Sebastian
Mora Flores, Erwin Wilfredo
Postigo, Jose Alberto
author_role author
author2 Barata Vallejo, Sebastian
Mora Flores, Erwin Wilfredo
Postigo, Jose Alberto
author2_role author
author
author
dc.subject.none.fl_str_mv PHOTOCATALYSIS
RADICAL CHAIN
topic PHOTOCATALYSIS
RADICAL CHAIN
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Photoinitiated perfluorobutylation reactions of 2-anisidine 1, propenyloxybenzene 2, and 2-mercaptoethanol 3 have been carried out employing commercially available n-C4F9I as the source of C4F9 radicals under three different photocatalysts (PCs) absorbing in the violet (Ir[dF(CF3)ppy]2(dtbbpy)+ (PC-1)), green (Rose Bengal (PC-2)) and red (zinc phthalocyanine PhZn (PC-3)) regions of the electromagnetic spectrum, in order to explore the quantum yields and radical chain lengths for each type of transformation and photoinitiated system. For substrates 1-3 and their different types of reactions, the comparative study between PCs seeks to establish the extent to which regioproducts, yields, and mechanistic proposals are influenced by the intervention of each PC. The different overall quantum yields and chain lengths obtained for each type of reaction under each PC are a direct consequence of the efficiency of the photoinitiation events, i.e., primary radical production, propagation and termination steps. This will have important implications in the understanding and representations of the mechanisms postulated, in terms of closed and open catalytic cycles. One strategy we apply to uncover radical propagating chains in our mechanisms is to explore photocatalysts that operate in oxidative and reductive quenching manners for each type of transformation.
Fil: Yerien, Damián Emilio. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina
Fil: Barata Vallejo, Sebastian. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Centre National de la Recherche Scientifique; Francia
Fil: Mora Flores, Erwin Wilfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina
Fil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina
description Photoinitiated perfluorobutylation reactions of 2-anisidine 1, propenyloxybenzene 2, and 2-mercaptoethanol 3 have been carried out employing commercially available n-C4F9I as the source of C4F9 radicals under three different photocatalysts (PCs) absorbing in the violet (Ir[dF(CF3)ppy]2(dtbbpy)+ (PC-1)), green (Rose Bengal (PC-2)) and red (zinc phthalocyanine PhZn (PC-3)) regions of the electromagnetic spectrum, in order to explore the quantum yields and radical chain lengths for each type of transformation and photoinitiated system. For substrates 1-3 and their different types of reactions, the comparative study between PCs seeks to establish the extent to which regioproducts, yields, and mechanistic proposals are influenced by the intervention of each PC. The different overall quantum yields and chain lengths obtained for each type of reaction under each PC are a direct consequence of the efficiency of the photoinitiation events, i.e., primary radical production, propagation and termination steps. This will have important implications in the understanding and representations of the mechanisms postulated, in terms of closed and open catalytic cycles. One strategy we apply to uncover radical propagating chains in our mechanisms is to explore photocatalysts that operate in oxidative and reductive quenching manners for each type of transformation.
publishDate 2020
dc.date.none.fl_str_mv 2020-08
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/11336/135011
Yerien, Damián Emilio; Barata Vallejo, Sebastian; Mora Flores, Erwin Wilfredo; Postigo, Jose Alberto; The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms; Royal Society of Chemistry; Catalysis Science & Technology; 10; 15; 8-2020; 5113-5128
2044-4761
2044-4761
CONICET Digital
CONICET
url http://hdl.handle.net/11336/135011
identifier_str_mv Yerien, Damián Emilio; Barata Vallejo, Sebastian; Mora Flores, Erwin Wilfredo; Postigo, Jose Alberto; The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms; Royal Society of Chemistry; Catalysis Science & Technology; 10; 15; 8-2020; 5113-5128
2044-4761
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2020/CY/D0CY00921K
info:eu-repo/semantics/altIdentifier/doi/10.1039/D0CY00921K
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
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
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score 13.070432

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