Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes)

Autores
Borkowski, Eduardo Jorge; Suvire, Fernando D.; Enriz, Ricardo Daniel
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The 13C chemical shifts of 15 pentacyclic terpenoids (fernenes) are compared to predicted 13C NMR chemical shifts obtained via empirically scaled GIAO shieldings. We report that accurate (rms error approx. 1.5 ppm) predictions of 13C chemical shifts can be achieved for these fernenes through the use of scaled shieldings calculated from GIAO theory with a relatively small basis set and on the basis of geometries obtained from DFT calculations. The best results (considering a reasonable cost-to-benefit ratio) were obtained from B3LYP/6-31G(d)//B3LYP/6-31G(d) computations. The chemical shifts anisotropy asymmetry (η was included in our calculations, enhancing the correlations between calculated and experimental chemical shifts. Our results indicate that the inclusion of a scaling factor allow to obtain an excellent correlation between δcalc and δexp. Also, the inclusion of asymmetry improves this correlation. In addition, taking into account the different conformations and the solvent effects a slight enhancement was obtained in this case.
Fil: Borkowski, Eduardo Jorge. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Suvire, Fernando D.. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina
Fil: Enriz, Ricardo Daniel. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
Materia
Fernenes
Dft/Giao Calculations
13c Chemical Shifts
Chemical Shifts Anisotropy
Nmr Calculations
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/14558
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/14558
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes)Borkowski, Eduardo JorgeSuvire, Fernando D.Enriz, Ricardo DanielFernenesDft/Giao Calculations13c Chemical ShiftsChemical Shifts AnisotropyNmr Calculationshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The 13C chemical shifts of 15 pentacyclic terpenoids (fernenes) are compared to predicted 13C NMR chemical shifts obtained via empirically scaled GIAO shieldings. We report that accurate (rms error approx. 1.5 ppm) predictions of 13C chemical shifts can be achieved for these fernenes through the use of scaled shieldings calculated from GIAO theory with a relatively small basis set and on the basis of geometries obtained from DFT calculations. The best results (considering a reasonable cost-to-benefit ratio) were obtained from B3LYP/6-31G(d)//B3LYP/6-31G(d) computations. The chemical shifts anisotropy asymmetry (η was included in our calculations, enhancing the correlations between calculated and experimental chemical shifts. Our results indicate that the inclusion of a scaling factor allow to obtain an excellent correlation between δcalc and δexp. Also, the inclusion of asymmetry improves this correlation. In addition, taking into account the different conformations and the solvent effects a slight enhancement was obtained in this case.Fil: Borkowski, Eduardo Jorge. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Suvire, Fernando D.. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; ArgentinaFil: Enriz, Ricardo Daniel. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; ArgentinaElsevier Science2010-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/14558Borkowski, Eduardo Jorge; Suvire, Fernando D.; Enriz, Ricardo Daniel; Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes); Elsevier Science; Journal Of Molecular Structure Theochem; 953; 1-3; 8-2010; 83-900166-1280enginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0166128010003222info:eu-repo/semantics/altIdentifier/doi/10.1016/j.theochem.2010.05.007info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:48:53Zoai:ri.conicet.gov.ar:11336/14558instacron: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:34982025-10-15 14:48:53.365CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes)
title Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes)
spellingShingle Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes)
Borkowski, Eduardo Jorge
Fernenes
Dft/Giao Calculations
13c Chemical Shifts
Chemical Shifts Anisotropy
Nmr Calculations
title_short Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes)
title_full Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes)
title_fullStr Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes)
title_full_unstemmed Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes)
title_sort Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes)
dc.creator.none.fl_str_mv Borkowski, Eduardo Jorge
Suvire, Fernando D.
Enriz, Ricardo Daniel
author Borkowski, Eduardo Jorge
author_facet Borkowski, Eduardo Jorge
Suvire, Fernando D.
Enriz, Ricardo Daniel
author_role author
author2 Suvire, Fernando D.
Enriz, Ricardo Daniel
author2_role author
author
dc.subject.none.fl_str_mv Fernenes
Dft/Giao Calculations
13c Chemical Shifts
Chemical Shifts Anisotropy
Nmr Calculations
topic Fernenes
Dft/Giao Calculations
13c Chemical Shifts
Chemical Shifts Anisotropy
Nmr Calculations
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The 13C chemical shifts of 15 pentacyclic terpenoids (fernenes) are compared to predicted 13C NMR chemical shifts obtained via empirically scaled GIAO shieldings. We report that accurate (rms error approx. 1.5 ppm) predictions of 13C chemical shifts can be achieved for these fernenes through the use of scaled shieldings calculated from GIAO theory with a relatively small basis set and on the basis of geometries obtained from DFT calculations. The best results (considering a reasonable cost-to-benefit ratio) were obtained from B3LYP/6-31G(d)//B3LYP/6-31G(d) computations. The chemical shifts anisotropy asymmetry (η was included in our calculations, enhancing the correlations between calculated and experimental chemical shifts. Our results indicate that the inclusion of a scaling factor allow to obtain an excellent correlation between δcalc and δexp. Also, the inclusion of asymmetry improves this correlation. In addition, taking into account the different conformations and the solvent effects a slight enhancement was obtained in this case.
Fil: Borkowski, Eduardo Jorge. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Suvire, Fernando D.. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina
Fil: Enriz, Ricardo Daniel. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
description The 13C chemical shifts of 15 pentacyclic terpenoids (fernenes) are compared to predicted 13C NMR chemical shifts obtained via empirically scaled GIAO shieldings. We report that accurate (rms error approx. 1.5 ppm) predictions of 13C chemical shifts can be achieved for these fernenes through the use of scaled shieldings calculated from GIAO theory with a relatively small basis set and on the basis of geometries obtained from DFT calculations. The best results (considering a reasonable cost-to-benefit ratio) were obtained from B3LYP/6-31G(d)//B3LYP/6-31G(d) computations. The chemical shifts anisotropy asymmetry (η was included in our calculations, enhancing the correlations between calculated and experimental chemical shifts. Our results indicate that the inclusion of a scaling factor allow to obtain an excellent correlation between δcalc and δexp. Also, the inclusion of asymmetry improves this correlation. In addition, taking into account the different conformations and the solvent effects a slight enhancement was obtained in this case.
publishDate 2010
dc.date.none.fl_str_mv 2010-08
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/11336/14558
Borkowski, Eduardo Jorge; Suvire, Fernando D.; Enriz, Ricardo Daniel; Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes); Elsevier Science; Journal Of Molecular Structure Theochem; 953; 1-3; 8-2010; 83-90
0166-1280
url http://hdl.handle.net/11336/14558
identifier_str_mv Borkowski, Eduardo Jorge; Suvire, Fernando D.; Enriz, Ricardo Daniel; Correlation Between Experimental and DFT/GIAO Computed 13C NMR Chemical Shifts. A Theoretical Study on Pentacyclic Terpenoids (fernenes); Elsevier Science; Journal Of Molecular Structure Theochem; 953; 1-3; 8-2010; 83-90
0166-1280
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0166128010003222
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.theochem.2010.05.007
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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 13.216834

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