DFT study on the cycloreversion of thietane radical cations

Autores
Domingo, Luis R.; Pérez-Ruiz, Rauíl; Argüello, Juan Elias; Miranda, Miguel A.
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4 + 2] cycloadducts are obtained. Thus, the CR of radical cations 1a,b •+ is initiated by C2-C3 bond breaking, giving common intermediates INa,b. At this stage, two reaction pathways are feasible involving ion molecule complexes IMCa,b (i) or radical cations 4a,b •+ (ii). Calculations support that 1a •+ follows reaction pathway ii (leading to the formal [4 + 2] cycloadducts 5a). By contrast, 1b •+ follows pathway i, leading to trans-stilbene radical cation (2b •+) and thiobenzophenone. © 2011 American Chemical Society.
Fil: Domingo, Luis R.. Universidad de Valencia; España
Fil: Pérez-Ruiz, Rauíl. Universidad Politécnica de Valencia; España
Fil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Miranda, Miguel A.. Universidad Politécnica de Valencia; España
Materia
Radical Cation
Ciclorevesion
Dft Calculation
Thietane
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:11336/65854
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/65854
network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling DFT study on the cycloreversion of thietane radical cationsDomingo, Luis R.Pérez-Ruiz, RauílArgüello, Juan EliasMiranda, Miguel A.Radical CationCiclorevesionDft CalculationThietanehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4 + 2] cycloadducts are obtained. Thus, the CR of radical cations 1a,b •+ is initiated by C2-C3 bond breaking, giving common intermediates INa,b. At this stage, two reaction pathways are feasible involving ion molecule complexes IMCa,b (i) or radical cations 4a,b •+ (ii). Calculations support that 1a •+ follows reaction pathway ii (leading to the formal [4 + 2] cycloadducts 5a). By contrast, 1b •+ follows pathway i, leading to trans-stilbene radical cation (2b •+) and thiobenzophenone. © 2011 American Chemical Society.Fil: Domingo, Luis R.. Universidad de Valencia; EspañaFil: Pérez-Ruiz, Rauíl. Universidad Politécnica de Valencia; EspañaFil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Miranda, Miguel A.. Universidad Politécnica de Valencia; EspañaAmerican Chemical Society2011-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/65854Domingo, Luis R.; Pérez-Ruiz, Rauíl; Argüello, Juan Elias; Miranda, Miguel A.; DFT study on the cycloreversion of thietane radical cations; American Chemical Society; Journal of Physical Chemistry A; 115; 21; 6-2011; 5443-54481089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp200177ainfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/jp200177ainfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:11:54Zoai:ri.conicet.gov.ar:11336/65854instacron: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 12:11:54.983CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv DFT study on the cycloreversion of thietane radical cations
title DFT study on the cycloreversion of thietane radical cations
spellingShingle DFT study on the cycloreversion of thietane radical cations
Domingo, Luis R.
Radical Cation
Ciclorevesion
Dft Calculation
Thietane
title_short DFT study on the cycloreversion of thietane radical cations
title_full DFT study on the cycloreversion of thietane radical cations
title_fullStr DFT study on the cycloreversion of thietane radical cations
title_full_unstemmed DFT study on the cycloreversion of thietane radical cations
title_sort DFT study on the cycloreversion of thietane radical cations
dc.creator.none.fl_str_mv Domingo, Luis R.
Pérez-Ruiz, Rauíl
Argüello, Juan Elias
Miranda, Miguel A.
author Domingo, Luis R.
author_facet Domingo, Luis R.
Pérez-Ruiz, Rauíl
Argüello, Juan Elias
Miranda, Miguel A.
author_role author
author2 Pérez-Ruiz, Rauíl
Argüello, Juan Elias
Miranda, Miguel A.
author2_role author
author
author
dc.subject.none.fl_str_mv Radical Cation
Ciclorevesion
Dft Calculation
Thietane
topic Radical Cation
Ciclorevesion
Dft Calculation
Thietane
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4 + 2] cycloadducts are obtained. Thus, the CR of radical cations 1a,b •+ is initiated by C2-C3 bond breaking, giving common intermediates INa,b. At this stage, two reaction pathways are feasible involving ion molecule complexes IMCa,b (i) or radical cations 4a,b •+ (ii). Calculations support that 1a •+ follows reaction pathway ii (leading to the formal [4 + 2] cycloadducts 5a). By contrast, 1b •+ follows pathway i, leading to trans-stilbene radical cation (2b •+) and thiobenzophenone. © 2011 American Chemical Society.
Fil: Domingo, Luis R.. Universidad de Valencia; España
Fil: Pérez-Ruiz, Rauíl. Universidad Politécnica de Valencia; España
Fil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Miranda, Miguel A.. Universidad Politécnica de Valencia; España
description The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4 + 2] cycloadducts are obtained. Thus, the CR of radical cations 1a,b •+ is initiated by C2-C3 bond breaking, giving common intermediates INa,b. At this stage, two reaction pathways are feasible involving ion molecule complexes IMCa,b (i) or radical cations 4a,b •+ (ii). Calculations support that 1a •+ follows reaction pathway ii (leading to the formal [4 + 2] cycloadducts 5a). By contrast, 1b •+ follows pathway i, leading to trans-stilbene radical cation (2b •+) and thiobenzophenone. © 2011 American Chemical Society.
publishDate 2011
dc.date.none.fl_str_mv 2011-06
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/11336/65854
Domingo, Luis R.; Pérez-Ruiz, Rauíl; Argüello, Juan Elias; Miranda, Miguel A.; DFT study on the cycloreversion of thietane radical cations; American Chemical Society; Journal of Physical Chemistry A; 115; 21; 6-2011; 5443-5448
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/65854
identifier_str_mv Domingo, Luis R.; Pérez-Ruiz, Rauíl; Argüello, Juan Elias; Miranda, Miguel A.; DFT study on the cycloreversion of thietane radical cations; American Chemical Society; Journal of Physical Chemistry A; 115; 21; 6-2011; 5443-5448
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jp200177a
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/jp200177a
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 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 12.982451

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