19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes

Autores
Ghiviriga, Ion; Zhang, Lianhao; Martinez, Henry; Contreras, Ruben Horacio; Tormena, Cláudio F.; Nodin, Laura; Dolbier Jr., William R.
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In the process of studying the chemistry of perfluoro[2.2]paracyclophanes (PFPCs), a novel class of compounds, it became necessary to identify some disubstituted products. To achieve this goal, we characterize in this work some monosubstituted PFPCs, identifying their 19F-19F coupling patterns, and establishing a methodology for the assignment of their 19F chemical shifts. The pattern of coupling constants indicates a skewed geometry in which the upper deck moves towards or away from the substituent, depending on the substituent electron-donor character and size. Quantum chemical calculations, performed at the HF/6-311 + G(d,p)//B3LYP/EPR-III level of theory, confirmed the conformations inferred from coupling constants and reproduced well the values of the couplings. Transmission mechanisms for the FC term of four-and five-bond 19F-19F couplings are discussed in detail. Understanding the conformational preferences of PFPCs and how they are reflected by the coupling constants facilitates the assignment of 19F chemical shifts in monosubstituted PFPCs and the identification of the disubstituted products. Copyright © 2011 John Wiley & Sons, Ltd.
Fil: Ghiviriga, Ion. University of Florida; Estados Unidos
Fil: Zhang, Lianhao. University of Florida; Estados Unidos
Fil: Martinez, Henry. University of Florida; Estados Unidos
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
Fil: Nodin, Laura. University of Florida; Estados Unidos
Fil: Dolbier Jr., William R.. University of Florida; Estados Unidos
Materia
19f Chemical Shifts
19f-19f Couplings
Conformation
Fccp-Cmo
Fermi Hole
Nmr
Paracyclophane
Perfluoro[2.2]Paracyclophane
Through-Space
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:11336/56984
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/56984
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanesGhiviriga, IonZhang, LianhaoMartinez, HenryContreras, Ruben HoracioTormena, Cláudio F.Nodin, LauraDolbier Jr., William R.19f Chemical Shifts19f-19f CouplingsConformationFccp-CmoFermi HoleNmrParacyclophanePerfluoro[2.2]ParacyclophaneThrough-Spacehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In the process of studying the chemistry of perfluoro[2.2]paracyclophanes (PFPCs), a novel class of compounds, it became necessary to identify some disubstituted products. To achieve this goal, we characterize in this work some monosubstituted PFPCs, identifying their 19F-19F coupling patterns, and establishing a methodology for the assignment of their 19F chemical shifts. The pattern of coupling constants indicates a skewed geometry in which the upper deck moves towards or away from the substituent, depending on the substituent electron-donor character and size. Quantum chemical calculations, performed at the HF/6-311 + G(d,p)//B3LYP/EPR-III level of theory, confirmed the conformations inferred from coupling constants and reproduced well the values of the couplings. Transmission mechanisms for the FC term of four-and five-bond 19F-19F couplings are discussed in detail. Understanding the conformational preferences of PFPCs and how they are reflected by the coupling constants facilitates the assignment of 19F chemical shifts in monosubstituted PFPCs and the identification of the disubstituted products. Copyright © 2011 John Wiley & Sons, Ltd.Fil: Ghiviriga, Ion. University of Florida; Estados UnidosFil: Zhang, Lianhao. University of Florida; Estados UnidosFil: Martinez, Henry. University of Florida; Estados UnidosFil: 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; BrasilFil: Nodin, Laura. University of Florida; Estados UnidosFil: Dolbier Jr., William R.. University of Florida; Estados UnidosJohn Wiley & Sons Ltd2011-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/56984Ghiviriga, Ion; Zhang, Lianhao; Martinez, Henry; Contreras, Ruben Horacio; Tormena, Cláudio F.; et al.; 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 49; 3; 2-2011; 93-1050749-1581CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/mrc.2713info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:11:20Zoai:ri.conicet.gov.ar:11336/56984instacron: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 11:11:20.49CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes
title 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes
spellingShingle 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes
Ghiviriga, Ion
19f Chemical Shifts
19f-19f Couplings
Conformation
Fccp-Cmo
Fermi Hole
Nmr
Paracyclophane
Perfluoro[2.2]Paracyclophane
Through-Space
title_short 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes
title_full 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes
title_fullStr 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes
title_full_unstemmed 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes
title_sort 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes
dc.creator.none.fl_str_mv Ghiviriga, Ion
Zhang, Lianhao
Martinez, Henry
Contreras, Ruben Horacio
Tormena, Cláudio F.
Nodin, Laura
Dolbier Jr., William R.
author Ghiviriga, Ion
author_facet Ghiviriga, Ion
Zhang, Lianhao
Martinez, Henry
Contreras, Ruben Horacio
Tormena, Cláudio F.
Nodin, Laura
Dolbier Jr., William R.
author_role author
author2 Zhang, Lianhao
Martinez, Henry
Contreras, Ruben Horacio
Tormena, Cláudio F.
Nodin, Laura
Dolbier Jr., William R.
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv 19f Chemical Shifts
19f-19f Couplings
Conformation
Fccp-Cmo
Fermi Hole
Nmr
Paracyclophane
Perfluoro[2.2]Paracyclophane
Through-Space
topic 19f Chemical Shifts
19f-19f Couplings
Conformation
Fccp-Cmo
Fermi Hole
Nmr
Paracyclophane
Perfluoro[2.2]Paracyclophane
Through-Space
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 the process of studying the chemistry of perfluoro[2.2]paracyclophanes (PFPCs), a novel class of compounds, it became necessary to identify some disubstituted products. To achieve this goal, we characterize in this work some monosubstituted PFPCs, identifying their 19F-19F coupling patterns, and establishing a methodology for the assignment of their 19F chemical shifts. The pattern of coupling constants indicates a skewed geometry in which the upper deck moves towards or away from the substituent, depending on the substituent electron-donor character and size. Quantum chemical calculations, performed at the HF/6-311 + G(d,p)//B3LYP/EPR-III level of theory, confirmed the conformations inferred from coupling constants and reproduced well the values of the couplings. Transmission mechanisms for the FC term of four-and five-bond 19F-19F couplings are discussed in detail. Understanding the conformational preferences of PFPCs and how they are reflected by the coupling constants facilitates the assignment of 19F chemical shifts in monosubstituted PFPCs and the identification of the disubstituted products. Copyright © 2011 John Wiley & Sons, Ltd.
Fil: Ghiviriga, Ion. University of Florida; Estados Unidos
Fil: Zhang, Lianhao. University of Florida; Estados Unidos
Fil: Martinez, Henry. University of Florida; Estados Unidos
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
Fil: Nodin, Laura. University of Florida; Estados Unidos
Fil: Dolbier Jr., William R.. University of Florida; Estados Unidos
description In the process of studying the chemistry of perfluoro[2.2]paracyclophanes (PFPCs), a novel class of compounds, it became necessary to identify some disubstituted products. To achieve this goal, we characterize in this work some monosubstituted PFPCs, identifying their 19F-19F coupling patterns, and establishing a methodology for the assignment of their 19F chemical shifts. The pattern of coupling constants indicates a skewed geometry in which the upper deck moves towards or away from the substituent, depending on the substituent electron-donor character and size. Quantum chemical calculations, performed at the HF/6-311 + G(d,p)//B3LYP/EPR-III level of theory, confirmed the conformations inferred from coupling constants and reproduced well the values of the couplings. Transmission mechanisms for the FC term of four-and five-bond 19F-19F couplings are discussed in detail. Understanding the conformational preferences of PFPCs and how they are reflected by the coupling constants facilitates the assignment of 19F chemical shifts in monosubstituted PFPCs and the identification of the disubstituted products. Copyright © 2011 John Wiley & Sons, Ltd.
publishDate 2011
dc.date.none.fl_str_mv 2011-02
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/11336/56984
Ghiviriga, Ion; Zhang, Lianhao; Martinez, Henry; Contreras, Ruben Horacio; Tormena, Cláudio F.; et al.; 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 49; 3; 2-2011; 93-105
0749-1581
CONICET Digital
CONICET
url http://hdl.handle.net/11336/56984
identifier_str_mv Ghiviriga, Ion; Zhang, Lianhao; Martinez, Henry; Contreras, Ruben Horacio; Tormena, Cláudio F.; et al.; 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 49; 3; 2-2011; 93-105
0749-1581
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/mrc.2713
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 12.982451

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