Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives

Autores
Vilcachagua, Janaina Dantas; Ducati, Lucas C.; Rittner, Roberto; Contreras, Ruben Horacio; Tormena, Cláudio F.
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of 1JCF NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH2; NO 2) is presented. The formulation of this approach is based on the influence of different conjugative and hyperconjugative interactions on a second-order property, which can be qualitatively predicted if it is 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 orbitals, which define some experimental trends for 1JCF spin-spin coupling constants. In addition, DFT hybrid functionals were used, and a similar degree of confidence to compute the 1JCF with those observed for the SOPPA(CCSD) method was obtained. The 1JCF SSCCs for ezetimibe, a commercially fluorinated drug used to reduce cholesterol levels, were measured and DFT-calculated, and the qualitative approach quoted above was applied. As a byproduct, a possible method to determine experimentally a significant PSO contribution to 1JCF SSCCs is discussed. © 2011 American Chemical Society.
Fil: Vilcachagua, Janaina Dantas. Universidade Estadual de Campinas; Brasil
Fil: Ducati, Lucas C.. Universidade Estadual de Campinas; Brasil
Fil: Rittner, Roberto. Universidade Estadual de Campinas; Brasil
Fil: Contreras, Ruben Horacio. Universidad de Buenos Aires; Argentina. 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
Nmr 2j(Cf) Couplings
Fluorobenzene Derivatives
Ortho Effect
Substituent Effects
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:11336/57206
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/57206
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivativesVilcachagua, Janaina DantasDucati, Lucas C.Rittner, RobertoContreras, Ruben HoracioTormena, Cláudio F.Nmr 2j(Cf) CouplingsFluorobenzene DerivativesOrtho EffectSubstituent Effectshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of 1JCF NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH2; NO 2) is presented. The formulation of this approach is based on the influence of different conjugative and hyperconjugative interactions on a second-order property, which can be qualitatively predicted if it is 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 orbitals, which define some experimental trends for 1JCF spin-spin coupling constants. In addition, DFT hybrid functionals were used, and a similar degree of confidence to compute the 1JCF with those observed for the SOPPA(CCSD) method was obtained. The 1JCF SSCCs for ezetimibe, a commercially fluorinated drug used to reduce cholesterol levels, were measured and DFT-calculated, and the qualitative approach quoted above was applied. As a byproduct, a possible method to determine experimentally a significant PSO contribution to 1JCF SSCCs is discussed. © 2011 American Chemical Society.Fil: Vilcachagua, Janaina Dantas. Universidade Estadual de Campinas; BrasilFil: Ducati, Lucas C.. Universidade Estadual de Campinas; BrasilFil: Rittner, Roberto. Universidade Estadual de Campinas; BrasilFil: Contreras, Ruben Horacio. Universidad de Buenos Aires; Argentina. 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 Society2011-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/57206Vilcachagua, Janaina Dantas; Ducati, Lucas C.; Rittner, Roberto; Contreras, Ruben Horacio; Tormena, Cláudio F.; Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives; American Chemical Society; Journal of Physical Chemistry A; 115; 7; 1-2011; 1272-12791089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp110290binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-26T09:04:46Zoai:ri.conicet.gov.ar:11336/57206instacron: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:34982025-11-26 09:04:46.411CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
title Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
spellingShingle Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
Vilcachagua, Janaina Dantas
Nmr 2j(Cf) Couplings
Fluorobenzene Derivatives
Ortho Effect
Substituent Effects
title_short Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
title_full Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
title_fullStr Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
title_full_unstemmed Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
title_sort Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
dc.creator.none.fl_str_mv Vilcachagua, Janaina Dantas
Ducati, Lucas C.
Rittner, Roberto
Contreras, Ruben Horacio
Tormena, Cláudio F.
author Vilcachagua, Janaina Dantas
author_facet Vilcachagua, Janaina Dantas
Ducati, Lucas C.
Rittner, Roberto
Contreras, Ruben Horacio
Tormena, Cláudio F.
author_role author
author2 Ducati, Lucas C.
Rittner, Roberto
Contreras, Ruben Horacio
Tormena, Cláudio F.
author2_role author
author
author
author
dc.subject.none.fl_str_mv Nmr 2j(Cf) Couplings
Fluorobenzene Derivatives
Ortho Effect
Substituent Effects
topic Nmr 2j(Cf) Couplings
Fluorobenzene Derivatives
Ortho Effect
Substituent Effects
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of 1JCF NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH2; NO 2) is presented. The formulation of this approach is based on the influence of different conjugative and hyperconjugative interactions on a second-order property, which can be qualitatively predicted if it is 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 orbitals, which define some experimental trends for 1JCF spin-spin coupling constants. In addition, DFT hybrid functionals were used, and a similar degree of confidence to compute the 1JCF with those observed for the SOPPA(CCSD) method was obtained. The 1JCF SSCCs for ezetimibe, a commercially fluorinated drug used to reduce cholesterol levels, were measured and DFT-calculated, and the qualitative approach quoted above was applied. As a byproduct, a possible method to determine experimentally a significant PSO contribution to 1JCF SSCCs is discussed. © 2011 American Chemical Society.
Fil: Vilcachagua, Janaina Dantas. Universidade Estadual de Campinas; Brasil
Fil: Ducati, Lucas C.. Universidade Estadual de Campinas; Brasil
Fil: Rittner, Roberto. Universidade Estadual de Campinas; Brasil
Fil: Contreras, Ruben Horacio. Universidad de Buenos Aires; Argentina. 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 Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of 1JCF NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH2; NO 2) is presented. The formulation of this approach is based on the influence of different conjugative and hyperconjugative interactions on a second-order property, which can be qualitatively predicted if it is 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 orbitals, which define some experimental trends for 1JCF spin-spin coupling constants. In addition, DFT hybrid functionals were used, and a similar degree of confidence to compute the 1JCF with those observed for the SOPPA(CCSD) method was obtained. The 1JCF SSCCs for ezetimibe, a commercially fluorinated drug used to reduce cholesterol levels, were measured and DFT-calculated, and the qualitative approach quoted above was applied. As a byproduct, a possible method to determine experimentally a significant PSO contribution to 1JCF SSCCs is discussed. © 2011 American Chemical Society.
publishDate 2011
dc.date.none.fl_str_mv 2011-01
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/11336/57206
Vilcachagua, Janaina Dantas; Ducati, Lucas C.; Rittner, Roberto; Contreras, Ruben Horacio; Tormena, Cláudio F.; Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives; American Chemical Society; Journal of Physical Chemistry A; 115; 7; 1-2011; 1272-1279
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/57206
identifier_str_mv Vilcachagua, Janaina Dantas; Ducati, Lucas C.; Rittner, Roberto; Contreras, Ruben Horacio; Tormena, Cláudio F.; Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives; American Chemical Society; Journal of Physical Chemistry A; 115; 7; 1-2011; 1272-1279
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/jp110290b
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 13.011256

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