Stereochemical dependence of NMR geminal spin-spin coupling constants

Autores
Contreras, Ruben Horacio; Provasi, Patricio Federico; Dos Santos, Francisco P.; Tormena, Claudio F.
Año de publicación
2008
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work it was sought to explore the versatility of germinal spin–spin coupling constants, ²JxySSCCs, as probes for stereochemical studies. A set of compounds, where their experimental ²JxySSCCs through the X–C–Y molecular fragment are predicted to be sensitive to hyperconjugative interactions involving either bonding or antibonding orbitals containing the C carbon atom (‘coupling pathway’), were analyzed. SSCC calculations were performed for some selected examples using the second order polarization propagator approximation (SOPPA) method or within the DFT-B3LYP framework. Hyperconjugative interactions were calculated within the Natural Bond Orbital (NBO) approach. Results are condensed in two qualitative rules: Rule Iм—hyperconjugative interactions transferring charge into the coupling pathway yield a positive increase to the Fermi contact (FC), contribution to ²Kxy reduced spin–spin coupling constants (RSSCC), and Rule IIм—hyperconjugative interactions transferring charge from the coupling pathway yield a negative increase to the FC contribution to ²Kxy RSSCC.
Fil: Contreras, Ruben Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina
Fil: Provasi, Patricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Fil: Dos Santos, Francisco P.. Universidad de Campinas. Instituto de Química; Brasil
Fil: Tormena, Claudio F.. Universidad de Campinas. Instituto de Química; Brasil
Materia
Geminal Couplings
Nmr
Fermi Contact
Stereochemistry
Geminal Spin–Spin Coupling Constants
Stereochemical Analysis
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:11336/24680
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/24680
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Stereochemical dependence of NMR geminal spin-spin coupling constantsContreras, Ruben HoracioProvasi, Patricio FedericoDos Santos, Francisco P.Tormena, Claudio F.Geminal CouplingsNmrFermi ContactStereochemistryGeminal Spin–Spin Coupling ConstantsStereochemical Analysishttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1In this work it was sought to explore the versatility of germinal spin–spin coupling constants, ²JxySSCCs, as probes for stereochemical studies. A set of compounds, where their experimental ²JxySSCCs through the X–C–Y molecular fragment are predicted to be sensitive to hyperconjugative interactions involving either bonding or antibonding orbitals containing the C carbon atom (‘coupling pathway’), were analyzed. SSCC calculations were performed for some selected examples using the second order polarization propagator approximation (SOPPA) method or within the DFT-B3LYP framework. Hyperconjugative interactions were calculated within the Natural Bond Orbital (NBO) approach. Results are condensed in two qualitative rules: Rule Iм—hyperconjugative interactions transferring charge into the coupling pathway yield a positive increase to the Fermi contact (FC), contribution to ²Kxy reduced spin–spin coupling constants (RSSCC), and Rule IIм—hyperconjugative interactions transferring charge from the coupling pathway yield a negative increase to the FC contribution to ²Kxy RSSCC.Fil: Contreras, Ruben Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; ArgentinaFil: Provasi, Patricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; ArgentinaFil: Dos Santos, Francisco P.. Universidad de Campinas. Instituto de Química; BrasilFil: Tormena, Claudio F.. Universidad de Campinas. Instituto de Química; BrasilJohn Wiley & Sons Ltd2008-12info: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/11336/24680Contreras, Ruben Horacio; Provasi, Patricio Federico; Dos Santos, Francisco P.; Tormena, Claudio F.; Stereochemical dependence of NMR geminal spin-spin coupling constants; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 47; 2; 12-2008; 113-1200749-15811097-458XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/mrc.2359info:eu-repo/semantics/altIdentifier/doi/10.1002/mrc.2359info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-05T10:26:38Zoai:ri.conicet.gov.ar:11336/24680instacron: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:34982025-11-05 10:26:38.659CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Stereochemical dependence of NMR geminal spin-spin coupling constants
title Stereochemical dependence of NMR geminal spin-spin coupling constants
spellingShingle Stereochemical dependence of NMR geminal spin-spin coupling constants
Contreras, Ruben Horacio
Geminal Couplings
Nmr
Fermi Contact
Stereochemistry
Geminal Spin–Spin Coupling Constants
Stereochemical Analysis
title_short Stereochemical dependence of NMR geminal spin-spin coupling constants
title_full Stereochemical dependence of NMR geminal spin-spin coupling constants
title_fullStr Stereochemical dependence of NMR geminal spin-spin coupling constants
title_full_unstemmed Stereochemical dependence of NMR geminal spin-spin coupling constants
title_sort Stereochemical dependence of NMR geminal spin-spin coupling constants
dc.creator.none.fl_str_mv Contreras, Ruben Horacio
Provasi, Patricio Federico
Dos Santos, Francisco P.
Tormena, Claudio F.
author Contreras, Ruben Horacio
author_facet Contreras, Ruben Horacio
Provasi, Patricio Federico
Dos Santos, Francisco P.
Tormena, Claudio F.
author_role author
author2 Provasi, Patricio Federico
Dos Santos, Francisco P.
Tormena, Claudio F.
author2_role author
author
author
dc.subject.none.fl_str_mv Geminal Couplings
Nmr
Fermi Contact
Stereochemistry
Geminal Spin–Spin Coupling Constants
Stereochemical Analysis
topic Geminal Couplings
Nmr
Fermi Contact
Stereochemistry
Geminal Spin–Spin Coupling Constants
Stereochemical Analysis
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In this work it was sought to explore the versatility of germinal spin–spin coupling constants, ²JxySSCCs, as probes for stereochemical studies. A set of compounds, where their experimental ²JxySSCCs through the X–C–Y molecular fragment are predicted to be sensitive to hyperconjugative interactions involving either bonding or antibonding orbitals containing the C carbon atom (‘coupling pathway’), were analyzed. SSCC calculations were performed for some selected examples using the second order polarization propagator approximation (SOPPA) method or within the DFT-B3LYP framework. Hyperconjugative interactions were calculated within the Natural Bond Orbital (NBO) approach. Results are condensed in two qualitative rules: Rule Iм—hyperconjugative interactions transferring charge into the coupling pathway yield a positive increase to the Fermi contact (FC), contribution to ²Kxy reduced spin–spin coupling constants (RSSCC), and Rule IIм—hyperconjugative interactions transferring charge from the coupling pathway yield a negative increase to the FC contribution to ²Kxy RSSCC.
Fil: Contreras, Ruben Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina
Fil: Provasi, Patricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Fil: Dos Santos, Francisco P.. Universidad de Campinas. Instituto de Química; Brasil
Fil: Tormena, Claudio F.. Universidad de Campinas. Instituto de Química; Brasil
description In this work it was sought to explore the versatility of germinal spin–spin coupling constants, ²JxySSCCs, as probes for stereochemical studies. A set of compounds, where their experimental ²JxySSCCs through the X–C–Y molecular fragment are predicted to be sensitive to hyperconjugative interactions involving either bonding or antibonding orbitals containing the C carbon atom (‘coupling pathway’), were analyzed. SSCC calculations were performed for some selected examples using the second order polarization propagator approximation (SOPPA) method or within the DFT-B3LYP framework. Hyperconjugative interactions were calculated within the Natural Bond Orbital (NBO) approach. Results are condensed in two qualitative rules: Rule Iм—hyperconjugative interactions transferring charge into the coupling pathway yield a positive increase to the Fermi contact (FC), contribution to ²Kxy reduced spin–spin coupling constants (RSSCC), and Rule IIм—hyperconjugative interactions transferring charge from the coupling pathway yield a negative increase to the FC contribution to ²Kxy RSSCC.
publishDate 2008
dc.date.none.fl_str_mv 2008-12
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/11336/24680
Contreras, Ruben Horacio; Provasi, Patricio Federico; Dos Santos, Francisco P.; Tormena, Claudio F.; Stereochemical dependence of NMR geminal spin-spin coupling constants; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 47; 2; 12-2008; 113-120
0749-1581
1097-458X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/24680
identifier_str_mv Contreras, Ruben Horacio; Provasi, Patricio Federico; Dos Santos, Francisco P.; Tormena, Claudio F.; Stereochemical dependence of NMR geminal spin-spin coupling constants; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 47; 2; 12-2008; 113-120
0749-1581
1097-458X
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://onlinelibrary.wiley.com/doi/10.1002/mrc.2359
info:eu-repo/semantics/altIdentifier/doi/10.1002/mrc.2359
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 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
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score 13.084122

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