A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications

Autores
Borosky, Gabriela Leonor; Okazaki, Takao; Laali, Kenneth K.
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
15N and 13C NMR chemical shifts were computed by GIAO-DFT and GIAO-MP2 for a series of p-substituted benzenediazonium mono- and dications in order to probe the electronic effects of the substituents on the diazonium moiety. Optimized geometries and N/N vibrational frequencies werealso considered for comparison. The GIAO-DFT derived15N chemical shifts correlate more closely with the experimental values as compared to GIAO-MP2. Energyminimizations at the B3LYP/6-311+G(2d,p), M062X-6-311+G(2d,p), MP2/6-311+G(2d,p), G2(MP2), and CBS-Q levels were carried out. Relative dication stability order HCO+ > HOMe+ > HN(Me) 2+ > HOH+ > HCN+ > HNO 2+ was derived from isodesmic proton transfer reactions. The Nβ-protonated dications were less stable than the corresponding p-R+ dications. Among the regioisomeric N β-protonated dications (with R = -F, -Cl, and -CN), those with the R group in the para position were preferred. For the regioisomeric, ring-protonated benzenium-diazonium dications, the meta-protonated dications were more favored (by DFT and MP2). Influence of the counterion and solvent on the computed 15N NMR chemical shifts in PhN2+ X- were also assessed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Fil: Borosky, Gabriela Leonor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Okazaki, Takao. Mie University; Japón
Fil: Laali, Kenneth K.. University of North Florida; Estados Unidos
Materia
Cations
Computer Chemistry
Counter Ion Effects
Density Functional Calculations
Diazonium Cations
Solvent Effects
Substituent Effects
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:11336/66343
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/66343
network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dicationsBorosky, Gabriela LeonorOkazaki, TakaoLaali, Kenneth K.CationsComputer ChemistryCounter Ion EffectsDensity Functional CalculationsDiazonium CationsSolvent EffectsSubstituent Effectshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/115N and 13C NMR chemical shifts were computed by GIAO-DFT and GIAO-MP2 for a series of p-substituted benzenediazonium mono- and dications in order to probe the electronic effects of the substituents on the diazonium moiety. Optimized geometries and N/N vibrational frequencies werealso considered for comparison. The GIAO-DFT derived15N chemical shifts correlate more closely with the experimental values as compared to GIAO-MP2. Energyminimizations at the B3LYP/6-311+G(2d,p), M062X-6-311+G(2d,p), MP2/6-311+G(2d,p), G2(MP2), and CBS-Q levels were carried out. Relative dication stability order HCO+ > HOMe+ > HN(Me) 2+ > HOH+ > HCN+ > HNO 2+ was derived from isodesmic proton transfer reactions. The Nβ-protonated dications were less stable than the corresponding p-R+ dications. Among the regioisomeric N β-protonated dications (with R = -F, -Cl, and -CN), those with the R group in the para position were preferred. For the regioisomeric, ring-protonated benzenium-diazonium dications, the meta-protonated dications were more favored (by DFT and MP2). Influence of the counterion and solvent on the computed 15N NMR chemical shifts in PhN2+ X- were also assessed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Fil: Borosky, Gabriela Leonor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Okazaki, Takao. Mie University; JapónFil: Laali, Kenneth K.. University of North Florida; Estados UnidosWiley VCH Verlag2011-02-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/66343Borosky, Gabriela Leonor; Okazaki, Takao; Laali, Kenneth K.; A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications; Wiley VCH Verlag; European Journal of Organic Chemistry; 2011; 9; 7-2-2011; 1771-17751434-193X1099-0690CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/ejoc.201001655info:eu-repo/semantics/altIdentifier/doi/10.1002/ejoc.201001655info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:17:04Zoai:ri.conicet.gov.ar:11336/66343instacron: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:34982025-09-10 13:17:04.712CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications
title A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications
spellingShingle A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications
Borosky, Gabriela Leonor
Cations
Computer Chemistry
Counter Ion Effects
Density Functional Calculations
Diazonium Cations
Solvent Effects
Substituent Effects
title_short A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications
title_full A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications
title_fullStr A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications
title_full_unstemmed A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications
title_sort A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications
dc.creator.none.fl_str_mv Borosky, Gabriela Leonor
Okazaki, Takao
Laali, Kenneth K.
author Borosky, Gabriela Leonor
author_facet Borosky, Gabriela Leonor
Okazaki, Takao
Laali, Kenneth K.
author_role author
author2 Okazaki, Takao
Laali, Kenneth K.
author2_role author
author
dc.subject.none.fl_str_mv Cations
Computer Chemistry
Counter Ion Effects
Density Functional Calculations
Diazonium Cations
Solvent Effects
Substituent Effects
topic Cations
Computer Chemistry
Counter Ion Effects
Density Functional Calculations
Diazonium Cations
Solvent Effects
Substituent Effects
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv 15N and 13C NMR chemical shifts were computed by GIAO-DFT and GIAO-MP2 for a series of p-substituted benzenediazonium mono- and dications in order to probe the electronic effects of the substituents on the diazonium moiety. Optimized geometries and N/N vibrational frequencies werealso considered for comparison. The GIAO-DFT derived15N chemical shifts correlate more closely with the experimental values as compared to GIAO-MP2. Energyminimizations at the B3LYP/6-311+G(2d,p), M062X-6-311+G(2d,p), MP2/6-311+G(2d,p), G2(MP2), and CBS-Q levels were carried out. Relative dication stability order HCO+ > HOMe+ > HN(Me) 2+ > HOH+ > HCN+ > HNO 2+ was derived from isodesmic proton transfer reactions. The Nβ-protonated dications were less stable than the corresponding p-R+ dications. Among the regioisomeric N β-protonated dications (with R = -F, -Cl, and -CN), those with the R group in the para position were preferred. For the regioisomeric, ring-protonated benzenium-diazonium dications, the meta-protonated dications were more favored (by DFT and MP2). Influence of the counterion and solvent on the computed 15N NMR chemical shifts in PhN2+ X- were also assessed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Fil: Borosky, Gabriela Leonor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Okazaki, Takao. Mie University; Japón
Fil: Laali, Kenneth K.. University of North Florida; Estados Unidos
description 15N and 13C NMR chemical shifts were computed by GIAO-DFT and GIAO-MP2 for a series of p-substituted benzenediazonium mono- and dications in order to probe the electronic effects of the substituents on the diazonium moiety. Optimized geometries and N/N vibrational frequencies werealso considered for comparison. The GIAO-DFT derived15N chemical shifts correlate more closely with the experimental values as compared to GIAO-MP2. Energyminimizations at the B3LYP/6-311+G(2d,p), M062X-6-311+G(2d,p), MP2/6-311+G(2d,p), G2(MP2), and CBS-Q levels were carried out. Relative dication stability order HCO+ > HOMe+ > HN(Me) 2+ > HOH+ > HCN+ > HNO 2+ was derived from isodesmic proton transfer reactions. The Nβ-protonated dications were less stable than the corresponding p-R+ dications. Among the regioisomeric N β-protonated dications (with R = -F, -Cl, and -CN), those with the R group in the para position were preferred. For the regioisomeric, ring-protonated benzenium-diazonium dications, the meta-protonated dications were more favored (by DFT and MP2). Influence of the counterion and solvent on the computed 15N NMR chemical shifts in PhN2+ X- were also assessed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
publishDate 2011
dc.date.none.fl_str_mv 2011-02-07
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/11336/66343
Borosky, Gabriela Leonor; Okazaki, Takao; Laali, Kenneth K.; A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications; Wiley VCH Verlag; European Journal of Organic Chemistry; 2011; 9; 7-2-2011; 1771-1775
1434-193X
1099-0690
CONICET Digital
CONICET
url http://hdl.handle.net/11336/66343
identifier_str_mv Borosky, Gabriela Leonor; Okazaki, Takao; Laali, Kenneth K.; A computational (DFT, MP2) and GIAO NMR study of substituent effects in benzenediazonium mono- and dications; Wiley VCH Verlag; European Journal of Organic Chemistry; 2011; 9; 7-2-2011; 1771-1775
1434-193X
1099-0690
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://onlinelibrary.wiley.com/doi/abs/10.1002/ejoc.201001655
info:eu-repo/semantics/altIdentifier/doi/10.1002/ejoc.201001655
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 Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
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 12.993085

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