A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized c...

Autores
Borosky, Gabriela Leonor; Laali, Kenneth K.
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Protonation reactions were studied by quantum-chemical theoretical methods (DFT and MP2) for a series of β,β-disubstituted vinyldiazonium cations (1+-14+), bearing stabilizing electron-releasing groups (H3CO-, (H3C)2N-, H3C-, (H 3C)3Si-, as well as halogens F, Cl). Taking into account the various mesomeric forms that these species can represent, protonations at Cα, at the β-substituent, and at Nβ were considered. The energetically most favored pathway in all cases was C α protonation, which formally corresponds to trapping of the mesomeric diazonium ylid. Based on the computed properties (optimized geometries, NPA-charge densities, and multinuclear GIAO-NMR chemical shifts), the resulting dications can best be viewed as carbenium/diazonium dications, in which the carbocation is further delocalized into the β-substituent. For the α-nitro derivative 15, protonation of the nitro group was predicted to be the most favored reaction, while Cα-and Nβ-protonation resulted in the loss of the nitronium ion.
Fil: Borosky, Gabriela Leonor. 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: Laali, Kenneth K.. University of North Florida. Department of Chemistry; Estados Unidos
Materia
Delocalized Carbenium/Diazonium Dications
Dft And Giao-Dft
Protonation
Substituent Effects
Trapping of Mesomeric Diazonium Ylid
Vinyldiazonium Cation
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:11336/71489
Acceder
id CONICETDig_642c5974ccc46d5f8756476a894d1a89
oai_identifier_str oai:ri.conicet.gov.ar:11336/71489
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dicationsBorosky, Gabriela LeonorLaali, Kenneth K.Delocalized Carbenium/Diazonium DicationsDft And Giao-DftProtonationSubstituent EffectsTrapping of Mesomeric Diazonium YlidVinyldiazonium Cationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Protonation reactions were studied by quantum-chemical theoretical methods (DFT and MP2) for a series of β,β-disubstituted vinyldiazonium cations (1+-14+), bearing stabilizing electron-releasing groups (H3CO-, (H3C)2N-, H3C-, (H 3C)3Si-, as well as halogens F, Cl). Taking into account the various mesomeric forms that these species can represent, protonations at Cα, at the β-substituent, and at Nβ were considered. The energetically most favored pathway in all cases was C α protonation, which formally corresponds to trapping of the mesomeric diazonium ylid. Based on the computed properties (optimized geometries, NPA-charge densities, and multinuclear GIAO-NMR chemical shifts), the resulting dications can best be viewed as carbenium/diazonium dications, in which the carbocation is further delocalized into the β-substituent. For the α-nitro derivative 15, protonation of the nitro group was predicted to be the most favored reaction, while Cα-and Nβ-protonation resulted in the loss of the nitronium ion.Fil: Borosky, Gabriela Leonor. 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: Laali, Kenneth K.. University of North Florida. Department of Chemistry; Estados UnidosJohn Wiley & Sons Ltd2010-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/71489Borosky, Gabriela Leonor; Laali, Kenneth K.; A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dications; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 23; 2; 2-2010; 115-1250894-32301099-1395CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/full/10.1002/poc.1588info:eu-repo/semantics/altIdentifier/doi/10.1002/poc.1588info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:24:06Zoai:ri.conicet.gov.ar:11336/71489instacron: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:34982025-09-10 13:24:07.055CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dications
title A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dications
spellingShingle A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dications
Borosky, Gabriela Leonor
Delocalized Carbenium/Diazonium Dications
Dft And Giao-Dft
Protonation
Substituent Effects
Trapping of Mesomeric Diazonium Ylid
Vinyldiazonium Cation
title_short A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dications
title_full A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dications
title_fullStr A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dications
title_full_unstemmed A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dications
title_sort A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dications
dc.creator.none.fl_str_mv Borosky, Gabriela Leonor
Laali, Kenneth K.
author Borosky, Gabriela Leonor
author_facet Borosky, Gabriela Leonor
Laali, Kenneth K.
author_role author
author2 Laali, Kenneth K.
author2_role author
dc.subject.none.fl_str_mv Delocalized Carbenium/Diazonium Dications
Dft And Giao-Dft
Protonation
Substituent Effects
Trapping of Mesomeric Diazonium Ylid
Vinyldiazonium Cation
topic Delocalized Carbenium/Diazonium Dications
Dft And Giao-Dft
Protonation
Substituent Effects
Trapping of Mesomeric Diazonium Ylid
Vinyldiazonium Cation
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Protonation reactions were studied by quantum-chemical theoretical methods (DFT and MP2) for a series of β,β-disubstituted vinyldiazonium cations (1+-14+), bearing stabilizing electron-releasing groups (H3CO-, (H3C)2N-, H3C-, (H 3C)3Si-, as well as halogens F, Cl). Taking into account the various mesomeric forms that these species can represent, protonations at Cα, at the β-substituent, and at Nβ were considered. The energetically most favored pathway in all cases was C α protonation, which formally corresponds to trapping of the mesomeric diazonium ylid. Based on the computed properties (optimized geometries, NPA-charge densities, and multinuclear GIAO-NMR chemical shifts), the resulting dications can best be viewed as carbenium/diazonium dications, in which the carbocation is further delocalized into the β-substituent. For the α-nitro derivative 15, protonation of the nitro group was predicted to be the most favored reaction, while Cα-and Nβ-protonation resulted in the loss of the nitronium ion.
Fil: Borosky, Gabriela Leonor. 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: Laali, Kenneth K.. University of North Florida. Department of Chemistry; Estados Unidos
description Protonation reactions were studied by quantum-chemical theoretical methods (DFT and MP2) for a series of β,β-disubstituted vinyldiazonium cations (1+-14+), bearing stabilizing electron-releasing groups (H3CO-, (H3C)2N-, H3C-, (H 3C)3Si-, as well as halogens F, Cl). Taking into account the various mesomeric forms that these species can represent, protonations at Cα, at the β-substituent, and at Nβ were considered. The energetically most favored pathway in all cases was C α protonation, which formally corresponds to trapping of the mesomeric diazonium ylid. Based on the computed properties (optimized geometries, NPA-charge densities, and multinuclear GIAO-NMR chemical shifts), the resulting dications can best be viewed as carbenium/diazonium dications, in which the carbocation is further delocalized into the β-substituent. For the α-nitro derivative 15, protonation of the nitro group was predicted to be the most favored reaction, while Cα-and Nβ-protonation resulted in the loss of the nitronium ion.
publishDate 2010
dc.date.none.fl_str_mv 2010-02
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/11336/71489
Borosky, Gabriela Leonor; Laali, Kenneth K.; A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dications; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 23; 2; 2-2010; 115-125
0894-3230
1099-1395
CONICET Digital
CONICET
url http://hdl.handle.net/11336/71489
identifier_str_mv Borosky, Gabriela Leonor; Laali, Kenneth K.; A computational study (DFT, MP2, and GIAO-DFT) of substituent effects on protonation regioselectivity in β,β-disubstituted vinyldiazonium cations: Formation of highly delocalized carbenium/diazonium dications; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 23; 2; 2-2010; 115-125
0894-3230
1099-1395
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://onlinelibrary.wiley.com/doi/full/10.1002/poc.1588
info:eu-repo/semantics/altIdentifier/doi/10.1002/poc.1588
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 John Wiley & Sons Ltd
publisher.none.fl_str_mv John Wiley & Sons Ltd
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_ 1842981335230054400
score 12.48226

Publicaciones similares