Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study

Autores
Neto, Alvaro Cunha; Ducati, Lucas C.; Rittner, Roberto; Tormena, Cláudio F.; Contreras, Ruben Horacio; Frenking, Gernot
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
As a first step, a qualitative analysis of the spin-orbit operator was performed to predict the kind of organic compounds, where it could be expected that the SO/FC (spin-orbit/Fermi contact) and SO/SD (spin-orbit/spin dipolar) yield unusually small contributions to the "heavy atom effect" on 13C SCSs (substituent chemical shifts). This analysis led to the conclusion that compounds presenting strong hyperconjugative interactions involving the σ*C-X orbital (X = halogen) are good examples where such effects can be expected to take place. On the basis of such results, the following set of model compounds was chosen: 2-eq-halocyclohexane (2-eq), 2-ax-halocyclohexane (2-ax), and 2-ax-halopyran (3), to measure 13C SCSs. Such experimental values, as well as those of methane and halomethanes taken from the literature, were compared to calculated values at a nonrelativistic approach using B3LYP, and at a relativistic approach with BP86 using scalar ZORA, spin-orbit ZORA, scalar PAULI, and spin-orbit PAULI. Results from relativistic calculations are in agreement with the trends predicted by the qualitative model discussed in this work. © 2009 American Chemical Society.
Fil: Neto, Alvaro Cunha. Universidade Estadual de Campinas; Brasil
Fil: Ducati, Lucas C.. Universidade Estadual de Campinas; Brasil
Fil: Rittner, Roberto. Universidade Estadual de Campinas; Brasil
Fil: Tormena, Cláudio F.. 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: Frenking, Gernot. Philipps-universität Marburg; Alemania
Materia
Heavy Atom Effect
Spin-Orbit
Hyperconjugative Interactions
13-C Chemical Shift
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:11336/61365
Acceder
id CONICETDig_e0f79a1ca34881de22feb4468f9430ad
oai_identifier_str oai:ri.conicet.gov.ar:11336/61365
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical studyNeto, Alvaro CunhaDucati, Lucas C.Rittner, RobertoTormena, Cláudio F.Contreras, Ruben HoracioFrenking, GernotHeavy Atom EffectSpin-OrbitHyperconjugative Interactions13-C Chemical Shifthttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1As a first step, a qualitative analysis of the spin-orbit operator was performed to predict the kind of organic compounds, where it could be expected that the SO/FC (spin-orbit/Fermi contact) and SO/SD (spin-orbit/spin dipolar) yield unusually small contributions to the "heavy atom effect" on 13C SCSs (substituent chemical shifts). This analysis led to the conclusion that compounds presenting strong hyperconjugative interactions involving the σ*C-X orbital (X = halogen) are good examples where such effects can be expected to take place. On the basis of such results, the following set of model compounds was chosen: 2-eq-halocyclohexane (2-eq), 2-ax-halocyclohexane (2-ax), and 2-ax-halopyran (3), to measure 13C SCSs. Such experimental values, as well as those of methane and halomethanes taken from the literature, were compared to calculated values at a nonrelativistic approach using B3LYP, and at a relativistic approach with BP86 using scalar ZORA, spin-orbit ZORA, scalar PAULI, and spin-orbit PAULI. Results from relativistic calculations are in agreement with the trends predicted by the qualitative model discussed in this work. © 2009 American Chemical Society.Fil: Neto, Alvaro Cunha. Universidade Estadual de Campinas; BrasilFil: Ducati, Lucas C.. Universidade Estadual de Campinas; BrasilFil: Rittner, Roberto. Universidade Estadual de Campinas; BrasilFil: Tormena, Cláudio F.. 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: Frenking, Gernot. Philipps-universität Marburg; AlemaniaAmerican Chemical Society2009-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/61365Neto, Alvaro Cunha; Ducati, Lucas C.; Rittner, Roberto; Tormena, Cláudio F.; Contreras, Ruben Horacio; et al.; Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study; American Chemical Society; Journal of Chemical Theory and Computation; 5; 9; 7-2009; 2222-22281549-9618CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/ct800520winfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:12:13Zoai:ri.conicet.gov.ar:11336/61365instacron: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 10:12:13.456CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study
title Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study
spellingShingle Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study
Neto, Alvaro Cunha
Heavy Atom Effect
Spin-Orbit
Hyperconjugative Interactions
13-C Chemical Shift
title_short Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study
title_full Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study
title_fullStr Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study
title_full_unstemmed Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study
title_sort Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study
dc.creator.none.fl_str_mv Neto, Alvaro Cunha
Ducati, Lucas C.
Rittner, Roberto
Tormena, Cláudio F.
Contreras, Ruben Horacio
Frenking, Gernot
author Neto, Alvaro Cunha
author_facet Neto, Alvaro Cunha
Ducati, Lucas C.
Rittner, Roberto
Tormena, Cláudio F.
Contreras, Ruben Horacio
Frenking, Gernot
author_role author
author2 Ducati, Lucas C.
Rittner, Roberto
Tormena, Cláudio F.
Contreras, Ruben Horacio
Frenking, Gernot
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Heavy Atom Effect
Spin-Orbit
Hyperconjugative Interactions
13-C Chemical Shift
topic Heavy Atom Effect
Spin-Orbit
Hyperconjugative Interactions
13-C Chemical Shift
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv As a first step, a qualitative analysis of the spin-orbit operator was performed to predict the kind of organic compounds, where it could be expected that the SO/FC (spin-orbit/Fermi contact) and SO/SD (spin-orbit/spin dipolar) yield unusually small contributions to the "heavy atom effect" on 13C SCSs (substituent chemical shifts). This analysis led to the conclusion that compounds presenting strong hyperconjugative interactions involving the σ*C-X orbital (X = halogen) are good examples where such effects can be expected to take place. On the basis of such results, the following set of model compounds was chosen: 2-eq-halocyclohexane (2-eq), 2-ax-halocyclohexane (2-ax), and 2-ax-halopyran (3), to measure 13C SCSs. Such experimental values, as well as those of methane and halomethanes taken from the literature, were compared to calculated values at a nonrelativistic approach using B3LYP, and at a relativistic approach with BP86 using scalar ZORA, spin-orbit ZORA, scalar PAULI, and spin-orbit PAULI. Results from relativistic calculations are in agreement with the trends predicted by the qualitative model discussed in this work. © 2009 American Chemical Society.
Fil: Neto, Alvaro Cunha. Universidade Estadual de Campinas; Brasil
Fil: Ducati, Lucas C.. Universidade Estadual de Campinas; Brasil
Fil: Rittner, Roberto. Universidade Estadual de Campinas; Brasil
Fil: Tormena, Cláudio F.. 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: Frenking, Gernot. Philipps-universität Marburg; Alemania
description As a first step, a qualitative analysis of the spin-orbit operator was performed to predict the kind of organic compounds, where it could be expected that the SO/FC (spin-orbit/Fermi contact) and SO/SD (spin-orbit/spin dipolar) yield unusually small contributions to the "heavy atom effect" on 13C SCSs (substituent chemical shifts). This analysis led to the conclusion that compounds presenting strong hyperconjugative interactions involving the σ*C-X orbital (X = halogen) are good examples where such effects can be expected to take place. On the basis of such results, the following set of model compounds was chosen: 2-eq-halocyclohexane (2-eq), 2-ax-halocyclohexane (2-ax), and 2-ax-halopyran (3), to measure 13C SCSs. Such experimental values, as well as those of methane and halomethanes taken from the literature, were compared to calculated values at a nonrelativistic approach using B3LYP, and at a relativistic approach with BP86 using scalar ZORA, spin-orbit ZORA, scalar PAULI, and spin-orbit PAULI. Results from relativistic calculations are in agreement with the trends predicted by the qualitative model discussed in this work. © 2009 American Chemical Society.
publishDate 2009
dc.date.none.fl_str_mv 2009-07
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/11336/61365
Neto, Alvaro Cunha; Ducati, Lucas C.; Rittner, Roberto; Tormena, Cláudio F.; Contreras, Ruben Horacio; et al.; Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study; American Chemical Society; Journal of Chemical Theory and Computation; 5; 9; 7-2009; 2222-2228
1549-9618
CONICET Digital
CONICET
url http://hdl.handle.net/11336/61365
identifier_str_mv Neto, Alvaro Cunha; Ducati, Lucas C.; Rittner, Roberto; Tormena, Cláudio F.; Contreras, Ruben Horacio; et al.; Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study; American Chemical Society; Journal of Chemical Theory and Computation; 5; 9; 7-2009; 2222-2228
1549-9618
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/ct800520w
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
_version_ 1844614027525750784
score 13.070432

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