The electronic origin of unusually large nJFN coupling constants in some Fluoroximes

Autores
Favaro, Denize C.; Contreras, Ruben Horacio; Tormena, Claudio F.
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
SOPPA(CCSD) calculations show that the FC term is the most important contribution to the through-space transmission of JFN coupling constants for the fluoroximes studied in this work. Because of the well-known behavior of FC term, a new rationalization for the experimental TSJFN SSCC is presented. It is mainly based on the overlap matrix (Sij) between fluorine and nitrogen lone pairs obtained from NBO analyses. An expression is proposed to take into account the influence of the electronic density (Dij) between coupled nuclei as well as the s% character at the site of the coupling nuclei of bonds and non-bonding electron pairs involved in Dij. In using this approach, a linear correlation between TSJFN versus Dij is obtained. The most important aspect of this rationalization is related to the facility for understanding the behavior of some unusual experimental coupling constants. It is shown that, at least in this case, the electronic origin of the so-called through-space coupling is transmitted through to the overlap of orbitals on the coupled atoms, suggesting that, at least for these compounds, instead of through-space coupling, it should better be dubbed as ‘through overlapping orbital coupling’.
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; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina
Fil: Tormena, Claudio F.. Universidade Estadual de Campinas; Brasil
Materia
NJFN THROUGH SPACE COUPLING CONSTANTS
DFN DEPENDENCE
LONE PAIRS INTERACTION
OVERLAP MATRIX
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:11336/2453
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/2453
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling The electronic origin of unusually large nJFN coupling constants in some FluoroximesFavaro, Denize C.Contreras, Ruben HoracioTormena, Claudio F.NJFN THROUGH SPACE COUPLING CONSTANTSDFN DEPENDENCELONE PAIRS INTERACTIONOVERLAP MATRIXhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1SOPPA(CCSD) calculations show that the FC term is the most important contribution to the through-space transmission of JFN coupling constants for the fluoroximes studied in this work. Because of the well-known behavior of FC term, a new rationalization for the experimental TSJFN SSCC is presented. It is mainly based on the overlap matrix (Sij) between fluorine and nitrogen lone pairs obtained from NBO analyses. An expression is proposed to take into account the influence of the electronic density (Dij) between coupled nuclei as well as the s% character at the site of the coupling nuclei of bonds and non-bonding electron pairs involved in Dij. In using this approach, a linear correlation between TSJFN versus Dij is obtained. The most important aspect of this rationalization is related to the facility for understanding the behavior of some unusual experimental coupling constants. It is shown that, at least in this case, the electronic origin of the so-called through-space coupling is transmitted through to the overlap of orbitals on the coupled atoms, suggesting that, at least for these compounds, instead of through-space coupling, it should better be dubbed as ‘through overlapping orbital coupling’.Fil: 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; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; ArgentinaFil: Tormena, Claudio F.. Universidade Estadual de Campinas; BrasilJohn Wiley & Sons Ltd2013-04-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/2453Favaro, Denize C.; Contreras, Ruben Horacio; Tormena, Claudio F.; The electronic origin of unusually large nJFN coupling constants in some Fluoroximes; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 51; 6; 4-4-2013; 334-3380749-1581enginfo:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/mrc.3950/abstractinfo:eu-repo/semantics/altIdentifier/doi/DOI:10.1002/mrc.3950info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:38:53Zoai:ri.conicet.gov.ar:11336/2453instacron: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 10:38:53.592CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The electronic origin of unusually large nJFN coupling constants in some Fluoroximes
title The electronic origin of unusually large nJFN coupling constants in some Fluoroximes
spellingShingle The electronic origin of unusually large nJFN coupling constants in some Fluoroximes
Favaro, Denize C.
NJFN THROUGH SPACE COUPLING CONSTANTS
DFN DEPENDENCE
LONE PAIRS INTERACTION
OVERLAP MATRIX
title_short The electronic origin of unusually large nJFN coupling constants in some Fluoroximes
title_full The electronic origin of unusually large nJFN coupling constants in some Fluoroximes
title_fullStr The electronic origin of unusually large nJFN coupling constants in some Fluoroximes
title_full_unstemmed The electronic origin of unusually large nJFN coupling constants in some Fluoroximes
title_sort The electronic origin of unusually large nJFN coupling constants in some Fluoroximes
dc.creator.none.fl_str_mv Favaro, Denize C.
Contreras, Ruben Horacio
Tormena, Claudio F.
author Favaro, Denize C.
author_facet Favaro, Denize C.
Contreras, Ruben Horacio
Tormena, Claudio F.
author_role author
author2 Contreras, Ruben Horacio
Tormena, Claudio F.
author2_role author
author
dc.subject.none.fl_str_mv NJFN THROUGH SPACE COUPLING CONSTANTS
DFN DEPENDENCE
LONE PAIRS INTERACTION
OVERLAP MATRIX
topic NJFN THROUGH SPACE COUPLING CONSTANTS
DFN DEPENDENCE
LONE PAIRS INTERACTION
OVERLAP MATRIX
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv SOPPA(CCSD) calculations show that the FC term is the most important contribution to the through-space transmission of JFN coupling constants for the fluoroximes studied in this work. Because of the well-known behavior of FC term, a new rationalization for the experimental TSJFN SSCC is presented. It is mainly based on the overlap matrix (Sij) between fluorine and nitrogen lone pairs obtained from NBO analyses. An expression is proposed to take into account the influence of the electronic density (Dij) between coupled nuclei as well as the s% character at the site of the coupling nuclei of bonds and non-bonding electron pairs involved in Dij. In using this approach, a linear correlation between TSJFN versus Dij is obtained. The most important aspect of this rationalization is related to the facility for understanding the behavior of some unusual experimental coupling constants. It is shown that, at least in this case, the electronic origin of the so-called through-space coupling is transmitted through to the overlap of orbitals on the coupled atoms, suggesting that, at least for these compounds, instead of through-space coupling, it should better be dubbed as ‘through overlapping orbital coupling’.
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; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina
Fil: Tormena, Claudio F.. Universidade Estadual de Campinas; Brasil
description SOPPA(CCSD) calculations show that the FC term is the most important contribution to the through-space transmission of JFN coupling constants for the fluoroximes studied in this work. Because of the well-known behavior of FC term, a new rationalization for the experimental TSJFN SSCC is presented. It is mainly based on the overlap matrix (Sij) between fluorine and nitrogen lone pairs obtained from NBO analyses. An expression is proposed to take into account the influence of the electronic density (Dij) between coupled nuclei as well as the s% character at the site of the coupling nuclei of bonds and non-bonding electron pairs involved in Dij. In using this approach, a linear correlation between TSJFN versus Dij is obtained. The most important aspect of this rationalization is related to the facility for understanding the behavior of some unusual experimental coupling constants. It is shown that, at least in this case, the electronic origin of the so-called through-space coupling is transmitted through to the overlap of orbitals on the coupled atoms, suggesting that, at least for these compounds, instead of through-space coupling, it should better be dubbed as ‘through overlapping orbital coupling’.
publishDate 2013
dc.date.none.fl_str_mv 2013-04-04
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/11336/2453
Favaro, Denize C.; Contreras, Ruben Horacio; Tormena, Claudio F.; The electronic origin of unusually large nJFN coupling constants in some Fluoroximes; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 51; 6; 4-4-2013; 334-338
0749-1581
url http://hdl.handle.net/11336/2453
identifier_str_mv Favaro, Denize C.; Contreras, Ruben Horacio; Tormena, Claudio F.; The electronic origin of unusually large nJFN coupling constants in some Fluoroximes; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 51; 6; 4-4-2013; 334-338
0749-1581
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.3950/abstract
info:eu-repo/semantics/altIdentifier/doi/DOI:10.1002/mrc.3950
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 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 13.070432

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