Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives

Autores
Anizelli, Pedro R.; Favaro, Denize C.; Contreras, Ruben Horacio; Tormena, Cláudio F.
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In order to study the influence of hyperconjugative, inductive, steric, and hydrogen-bond interactions on 1 JCF and 2 JCF NMR spin spin coupling constants (SSCCs), they were measured in cis- and trans-4-t-butyl-2-fluorocyclohexanones and their alcohol derivatives. The four isotropic terms of those SSCCs, Fermi contact (FC), spin dipolar (SD), paramagnetic spin orbit (PSO), and diamagnetic spin orbit (DSO), were calculated at the SOPPA(CCSD)/EPR-III level. Significant changes in FC and PSO terms along that series of compounds were rationalized in terms of their transmission mechanisms by employing a qualitative analysis of their expressions in terms of the polarization propagator formalism. The PSO term is found to be sensitive to proximate interactions like steric compression and hydrogen bonding; we describe how it could be used to gauge such interactions. The FC term of 2 JCF SSCC in cis4-t-butyl-2-fluorocyclohexanone is rationalized as transmitted in part by the superposition of the F and O electronic clouds.
Fil: Anizelli, Pedro R.. Universidade Estadual de Campinas; Brasil
Fil: Favaro, Denize C.. Universidade Estadual de Campinas; Brasil
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: Tormena, Cláudio F.. Universidade Estadual de Campinas; Brasil
Materia
ONE AND TWO-BOND J(CF) COUPLINGS
FLUOROCYCLOHEXANONES
ELECTRONIC INTERACTIONS
REAR BOND EFFECT
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:11336/268221
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/268221
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol DerivativesAnizelli, Pedro R.Favaro, Denize C.Contreras, Ruben HoracioTormena, Cláudio F.ONE AND TWO-BOND J(CF) COUPLINGSFLUOROCYCLOHEXANONESELECTRONIC INTERACTIONSREAR BOND EFFECThttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In order to study the influence of hyperconjugative, inductive, steric, and hydrogen-bond interactions on 1 JCF and 2 JCF NMR spin spin coupling constants (SSCCs), they were measured in cis- and trans-4-t-butyl-2-fluorocyclohexanones and their alcohol derivatives. The four isotropic terms of those SSCCs, Fermi contact (FC), spin dipolar (SD), paramagnetic spin orbit (PSO), and diamagnetic spin orbit (DSO), were calculated at the SOPPA(CCSD)/EPR-III level. Significant changes in FC and PSO terms along that series of compounds were rationalized in terms of their transmission mechanisms by employing a qualitative analysis of their expressions in terms of the polarization propagator formalism. The PSO term is found to be sensitive to proximate interactions like steric compression and hydrogen bonding; we describe how it could be used to gauge such interactions. The FC term of 2 JCF SSCC in cis4-t-butyl-2-fluorocyclohexanone is rationalized as transmitted in part by the superposition of the F and O electronic clouds.Fil: Anizelli, Pedro R.. Universidade Estadual de Campinas; BrasilFil: Favaro, Denize C.. Universidade Estadual de Campinas; BrasilFil: 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: Tormena, Cláudio F.. Universidade Estadual de Campinas; BrasilAmerican Chemical Society2011-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/268221Anizelli, Pedro R.; Favaro, Denize C.; Contreras, Ruben Horacio; Tormena, Cláudio F.; Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives; American Chemical Society; Journal of Physical Chemistry A; 115; 22; 5-2011; 5684-56921089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp202592cinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp202592cinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:54:27Zoai:ri.conicet.gov.ar:11336/268221instacron: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:34982025-10-22 11:54:28.128CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives
title Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives
spellingShingle Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives
Anizelli, Pedro R.
ONE AND TWO-BOND J(CF) COUPLINGS
FLUOROCYCLOHEXANONES
ELECTRONIC INTERACTIONS
REAR BOND EFFECT
title_short Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives
title_full Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives
title_fullStr Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives
title_full_unstemmed Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives
title_sort Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives
dc.creator.none.fl_str_mv Anizelli, Pedro R.
Favaro, Denize C.
Contreras, Ruben Horacio
Tormena, Cláudio F.
author Anizelli, Pedro R.
author_facet Anizelli, Pedro R.
Favaro, Denize C.
Contreras, Ruben Horacio
Tormena, Cláudio F.
author_role author
author2 Favaro, Denize C.
Contreras, Ruben Horacio
Tormena, Cláudio F.
author2_role author
author
author
dc.subject.none.fl_str_mv ONE AND TWO-BOND J(CF) COUPLINGS
FLUOROCYCLOHEXANONES
ELECTRONIC INTERACTIONS
REAR BOND EFFECT
topic ONE AND TWO-BOND J(CF) COUPLINGS
FLUOROCYCLOHEXANONES
ELECTRONIC INTERACTIONS
REAR BOND EFFECT
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In order to study the influence of hyperconjugative, inductive, steric, and hydrogen-bond interactions on 1 JCF and 2 JCF NMR spin spin coupling constants (SSCCs), they were measured in cis- and trans-4-t-butyl-2-fluorocyclohexanones and their alcohol derivatives. The four isotropic terms of those SSCCs, Fermi contact (FC), spin dipolar (SD), paramagnetic spin orbit (PSO), and diamagnetic spin orbit (DSO), were calculated at the SOPPA(CCSD)/EPR-III level. Significant changes in FC and PSO terms along that series of compounds were rationalized in terms of their transmission mechanisms by employing a qualitative analysis of their expressions in terms of the polarization propagator formalism. The PSO term is found to be sensitive to proximate interactions like steric compression and hydrogen bonding; we describe how it could be used to gauge such interactions. The FC term of 2 JCF SSCC in cis4-t-butyl-2-fluorocyclohexanone is rationalized as transmitted in part by the superposition of the F and O electronic clouds.
Fil: Anizelli, Pedro R.. Universidade Estadual de Campinas; Brasil
Fil: Favaro, Denize C.. Universidade Estadual de Campinas; Brasil
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: Tormena, Cláudio F.. Universidade Estadual de Campinas; Brasil
description In order to study the influence of hyperconjugative, inductive, steric, and hydrogen-bond interactions on 1 JCF and 2 JCF NMR spin spin coupling constants (SSCCs), they were measured in cis- and trans-4-t-butyl-2-fluorocyclohexanones and their alcohol derivatives. The four isotropic terms of those SSCCs, Fermi contact (FC), spin dipolar (SD), paramagnetic spin orbit (PSO), and diamagnetic spin orbit (DSO), were calculated at the SOPPA(CCSD)/EPR-III level. Significant changes in FC and PSO terms along that series of compounds were rationalized in terms of their transmission mechanisms by employing a qualitative analysis of their expressions in terms of the polarization propagator formalism. The PSO term is found to be sensitive to proximate interactions like steric compression and hydrogen bonding; we describe how it could be used to gauge such interactions. The FC term of 2 JCF SSCC in cis4-t-butyl-2-fluorocyclohexanone is rationalized as transmitted in part by the superposition of the F and O electronic clouds.
publishDate 2011
dc.date.none.fl_str_mv 2011-05
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/11336/268221
Anizelli, Pedro R.; Favaro, Denize C.; Contreras, Ruben Horacio; Tormena, Cláudio F.; Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives; American Chemical Society; Journal of Physical Chemistry A; 115; 22; 5-2011; 5684-5692
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/268221
identifier_str_mv Anizelli, Pedro R.; Favaro, Denize C.; Contreras, Ruben Horacio; Tormena, Cláudio F.; Effect of Electronic Interactions on NMR 1 J CF and 2 J CF Couplings in cis - and trans -4- t -Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives; American Chemical Society; Journal of Physical Chemistry A; 115; 22; 5-2011; 5684-5692
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/url/https://pubs.acs.org/doi/10.1021/jp202592c
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp202592c
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 12.982451

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