Qualitative study of substituent effects on NMR15N and 17O chemical shifts

Autores
Contreras, Ruben Horacio; Llorente, Tomás; Pagola, Gabriel Ignacio; Bustamante Pilone, Manuel Guillermo; Pasqualini, Enrique E.; Melo, Juan Ignacio; Tormena, Cláudio F.
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A qualitative approach to analyze the electronic origin of substituent effects on the paramagnetic part of chemical shifts is described and applied to few model systems, where its potentiality can be appreciated. The formulation of this approach is based on the following grounds. The influence of different inter- or intramolecular interactions on a second-order property can be qualitatively predicted if it can be known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitais that define some experimental trends of magnetic shielding constants. This approach is applied first to study the electronic origin of methyl-β substituent effects on both 15N and 17O chemical shifts, and afterward it is applied to a couple of examples of long-range substituent effects originated in charge transfer interactions such as the conjugative effect in aromatic compounds and σ-hyperconjugative interactions in saturated multicyclic compounds. © 2009 American Chemical Society.
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: Llorente, Tomás. Universidad de Buenos Aires; Argentina
Fil: Pagola, Gabriel Ignacio. 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: Bustamante Pilone, Manuel Guillermo. Universidad de Buenos Aires; Argentina
Fil: Pasqualini, Enrique E.. Comisión Nacional de Energía Atómica; Argentina
Fil: Melo, Juan Ignacio. 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: Tormena, Cláudio F.. Universidade Estadual de Campinas; Brasil
Materia
1,3-Dithiane
Hyperconjugative Interactions
Fermi Contact
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:11336/61364
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/61364
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Qualitative study of substituent effects on NMR15N and 17O chemical shiftsContreras, Ruben HoracioLlorente, TomásPagola, Gabriel IgnacioBustamante Pilone, Manuel GuillermoPasqualini, Enrique E.Melo, Juan IgnacioTormena, Cláudio F.1,3-DithianeHyperconjugative InteractionsFermi Contacthttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1A qualitative approach to analyze the electronic origin of substituent effects on the paramagnetic part of chemical shifts is described and applied to few model systems, where its potentiality can be appreciated. The formulation of this approach is based on the following grounds. The influence of different inter- or intramolecular interactions on a second-order property can be qualitatively predicted if it can be known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitais that define some experimental trends of magnetic shielding constants. This approach is applied first to study the electronic origin of methyl-β substituent effects on both 15N and 17O chemical shifts, and afterward it is applied to a couple of examples of long-range substituent effects originated in charge transfer interactions such as the conjugative effect in aromatic compounds and σ-hyperconjugative interactions in saturated multicyclic compounds. © 2009 American Chemical Society.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: Llorente, Tomás. Universidad de Buenos Aires; ArgentinaFil: Pagola, Gabriel Ignacio. 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: Bustamante Pilone, Manuel Guillermo. Universidad de Buenos Aires; ArgentinaFil: Pasqualini, Enrique E.. Comisión Nacional de Energía Atómica; ArgentinaFil: Melo, Juan Ignacio. 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: Tormena, Cláudio F.. Universidade Estadual de Campinas; BrasilAmerican Chemical Society2009-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/61364Contreras, Ruben Horacio; Llorente, Tomás; Pagola, Gabriel Ignacio; Bustamante Pilone, Manuel Guillermo; Pasqualini, Enrique E.; et al.; Qualitative study of substituent effects on NMR15N and 17O chemical shifts; American Chemical Society; Journal of Physical Chemistry A; 113; 36; 8-2009; 9874-98801089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp901926pinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:48:51Zoai:ri.conicet.gov.ar:11336/61364instacron: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 09:48:52.116CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Qualitative study of substituent effects on NMR15N and 17O chemical shifts
title Qualitative study of substituent effects on NMR15N and 17O chemical shifts
spellingShingle Qualitative study of substituent effects on NMR15N and 17O chemical shifts
Contreras, Ruben Horacio
1,3-Dithiane
Hyperconjugative Interactions
Fermi Contact
title_short Qualitative study of substituent effects on NMR15N and 17O chemical shifts
title_full Qualitative study of substituent effects on NMR15N and 17O chemical shifts
title_fullStr Qualitative study of substituent effects on NMR15N and 17O chemical shifts
title_full_unstemmed Qualitative study of substituent effects on NMR15N and 17O chemical shifts
title_sort Qualitative study of substituent effects on NMR15N and 17O chemical shifts
dc.creator.none.fl_str_mv Contreras, Ruben Horacio
Llorente, Tomás
Pagola, Gabriel Ignacio
Bustamante Pilone, Manuel Guillermo
Pasqualini, Enrique E.
Melo, Juan Ignacio
Tormena, Cláudio F.
author Contreras, Ruben Horacio
author_facet Contreras, Ruben Horacio
Llorente, Tomás
Pagola, Gabriel Ignacio
Bustamante Pilone, Manuel Guillermo
Pasqualini, Enrique E.
Melo, Juan Ignacio
Tormena, Cláudio F.
author_role author
author2 Llorente, Tomás
Pagola, Gabriel Ignacio
Bustamante Pilone, Manuel Guillermo
Pasqualini, Enrique E.
Melo, Juan Ignacio
Tormena, Cláudio F.
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv 1,3-Dithiane
Hyperconjugative Interactions
Fermi Contact
topic 1,3-Dithiane
Hyperconjugative Interactions
Fermi Contact
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv A qualitative approach to analyze the electronic origin of substituent effects on the paramagnetic part of chemical shifts is described and applied to few model systems, where its potentiality can be appreciated. The formulation of this approach is based on the following grounds. The influence of different inter- or intramolecular interactions on a second-order property can be qualitatively predicted if it can be known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitais that define some experimental trends of magnetic shielding constants. This approach is applied first to study the electronic origin of methyl-β substituent effects on both 15N and 17O chemical shifts, and afterward it is applied to a couple of examples of long-range substituent effects originated in charge transfer interactions such as the conjugative effect in aromatic compounds and σ-hyperconjugative interactions in saturated multicyclic compounds. © 2009 American Chemical Society.
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: Llorente, Tomás. Universidad de Buenos Aires; Argentina
Fil: Pagola, Gabriel Ignacio. 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: Bustamante Pilone, Manuel Guillermo. Universidad de Buenos Aires; Argentina
Fil: Pasqualini, Enrique E.. Comisión Nacional de Energía Atómica; Argentina
Fil: Melo, Juan Ignacio. 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: Tormena, Cláudio F.. Universidade Estadual de Campinas; Brasil
description A qualitative approach to analyze the electronic origin of substituent effects on the paramagnetic part of chemical shifts is described and applied to few model systems, where its potentiality can be appreciated. The formulation of this approach is based on the following grounds. The influence of different inter- or intramolecular interactions on a second-order property can be qualitatively predicted if it can be known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitais that define some experimental trends of magnetic shielding constants. This approach is applied first to study the electronic origin of methyl-β substituent effects on both 15N and 17O chemical shifts, and afterward it is applied to a couple of examples of long-range substituent effects originated in charge transfer interactions such as the conjugative effect in aromatic compounds and σ-hyperconjugative interactions in saturated multicyclic compounds. © 2009 American Chemical Society.
publishDate 2009
dc.date.none.fl_str_mv 2009-08
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/11336/61364
Contreras, Ruben Horacio; Llorente, Tomás; Pagola, Gabriel Ignacio; Bustamante Pilone, Manuel Guillermo; Pasqualini, Enrique E.; et al.; Qualitative study of substituent effects on NMR15N and 17O chemical shifts; American Chemical Society; Journal of Physical Chemistry A; 113; 36; 8-2009; 9874-9880
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/61364
identifier_str_mv Contreras, Ruben Horacio; Llorente, Tomás; Pagola, Gabriel Ignacio; Bustamante Pilone, Manuel Guillermo; Pasqualini, Enrique E.; et al.; Qualitative study of substituent effects on NMR15N and 17O chemical shifts; American Chemical Society; Journal of Physical Chemistry A; 113; 36; 8-2009; 9874-9880
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/jp901926p
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 13.070432

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