Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2

Autores
Sosa Carrizo, Daiann; Fernández, Israel; Martín, Sandra Elizabeth
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The formation of C–heteroatom bonds through the Stille cross-coupling reaction has been explored computationally within the density functional theory framework. To this end, the reaction profiles of the processes involving different aryl halides (PhCl, PhI) and heterostannanes (Me3SnZR2, Z = As, P; R = Ph, Me) in the presence of palladium catalyst have been investigated and compared to gain more insight into the differential reactivity observed experimentally. In addition, the main features of the reaction steps where the heterostannanes are involved, namely, the transmetalation and reductive elimination reactions, have been analyzed in detail. It was found that the overall relative reaction profile for the transmetalation step involving heterostannanes with Z = P is energetically favored over that involving species having Z = As, which agrees with the experimental observations. This can be mainly ascribed to the relative strength of the Sn–Z bond, which is broken during the transmetalation step (Sn–P < Sn–As).
Fil: Sosa Carrizo, Daiann. 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: Fernández, Israel. Universidad Complutense de Madrid. Facultad de Cs.químicas; España
Fil: Martín, Sandra Elizabeth. 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
Materia
Stille
Heterostannanes
Dft
Transmetalation
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:11336/31372
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2Sosa Carrizo, DaiannFernández, IsraelMartín, Sandra ElizabethStilleHeterostannanesDftTransmetalationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The formation of C–heteroatom bonds through the Stille cross-coupling reaction has been explored computationally within the density functional theory framework. To this end, the reaction profiles of the processes involving different aryl halides (PhCl, PhI) and heterostannanes (Me3SnZR2, Z = As, P; R = Ph, Me) in the presence of palladium catalyst have been investigated and compared to gain more insight into the differential reactivity observed experimentally. In addition, the main features of the reaction steps where the heterostannanes are involved, namely, the transmetalation and reductive elimination reactions, have been analyzed in detail. It was found that the overall relative reaction profile for the transmetalation step involving heterostannanes with Z = P is energetically favored over that involving species having Z = As, which agrees with the experimental observations. This can be mainly ascribed to the relative strength of the Sn–Z bond, which is broken during the transmetalation step (Sn–P < Sn–As).Fil: Sosa Carrizo, Daiann. 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: Fernández, Israel. Universidad Complutense de Madrid. Facultad de Cs.químicas; EspañaFil: Martín, Sandra Elizabeth. 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; ArgentinaAmerican Chemical Society2014-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/31372Sosa Carrizo, Daiann; Fernández, Israel; Martín, Sandra Elizabeth; Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2; American Chemical Society; Organometallics; 34; 1; 12-2014; 159-1660276-7333CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/om501027sinfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/om501027sinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:08:22Zoai:ri.conicet.gov.ar:11336/31372instacron: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:34982025-09-03 10:08:22.343CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2
title Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2
spellingShingle Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2
Sosa Carrizo, Daiann
Stille
Heterostannanes
Dft
Transmetalation
title_short Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2
title_full Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2
title_fullStr Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2
title_full_unstemmed Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2
title_sort Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2
dc.creator.none.fl_str_mv Sosa Carrizo, Daiann
Fernández, Israel
Martín, Sandra Elizabeth
author Sosa Carrizo, Daiann
author_facet Sosa Carrizo, Daiann
Fernández, Israel
Martín, Sandra Elizabeth
author_role author
author2 Fernández, Israel
Martín, Sandra Elizabeth
author2_role author
author
dc.subject.none.fl_str_mv Stille
Heterostannanes
Dft
Transmetalation
topic Stille
Heterostannanes
Dft
Transmetalation
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 formation of C–heteroatom bonds through the Stille cross-coupling reaction has been explored computationally within the density functional theory framework. To this end, the reaction profiles of the processes involving different aryl halides (PhCl, PhI) and heterostannanes (Me3SnZR2, Z = As, P; R = Ph, Me) in the presence of palladium catalyst have been investigated and compared to gain more insight into the differential reactivity observed experimentally. In addition, the main features of the reaction steps where the heterostannanes are involved, namely, the transmetalation and reductive elimination reactions, have been analyzed in detail. It was found that the overall relative reaction profile for the transmetalation step involving heterostannanes with Z = P is energetically favored over that involving species having Z = As, which agrees with the experimental observations. This can be mainly ascribed to the relative strength of the Sn–Z bond, which is broken during the transmetalation step (Sn–P < Sn–As).
Fil: Sosa Carrizo, Daiann. 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: Fernández, Israel. Universidad Complutense de Madrid. Facultad de Cs.químicas; España
Fil: Martín, Sandra Elizabeth. 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
description The formation of C–heteroatom bonds through the Stille cross-coupling reaction has been explored computationally within the density functional theory framework. To this end, the reaction profiles of the processes involving different aryl halides (PhCl, PhI) and heterostannanes (Me3SnZR2, Z = As, P; R = Ph, Me) in the presence of palladium catalyst have been investigated and compared to gain more insight into the differential reactivity observed experimentally. In addition, the main features of the reaction steps where the heterostannanes are involved, namely, the transmetalation and reductive elimination reactions, have been analyzed in detail. It was found that the overall relative reaction profile for the transmetalation step involving heterostannanes with Z = P is energetically favored over that involving species having Z = As, which agrees with the experimental observations. This can be mainly ascribed to the relative strength of the Sn–Z bond, which is broken during the transmetalation step (Sn–P < Sn–As).
publishDate 2014
dc.date.none.fl_str_mv 2014-12
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/11336/31372
Sosa Carrizo, Daiann; Fernández, Israel; Martín, Sandra Elizabeth; Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2; American Chemical Society; Organometallics; 34; 1; 12-2014; 159-166
0276-7333
CONICET Digital
CONICET
url http://hdl.handle.net/11336/31372
identifier_str_mv Sosa Carrizo, Daiann; Fernández, Israel; Martín, Sandra Elizabeth; Computational Study on the C–Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2; American Chemical Society; Organometallics; 34; 1; 12-2014; 159-166
0276-7333
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/om501027s
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/om501027s
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
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
_version_ 1842270041872007168
score 13.13397

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