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dc.contributor.CRUESPUNIVERSIDADE DE ESTADUAL DE CAMPINASpt_BR
dc.typeArtigo de periódicopt_BR
dc.titleNmr Spectroscopy And Theoretical Calculations In The Conformational Analysis Of 1-methylpyrrolidin-2-one 3-halo-derivativespt_BR
dc.contributor.authorde Melopt_BR
dc.contributor.authorUlisses Zonta; Silvapt_BR
dc.contributor.authorRai G. M.; Yamazakipt_BR
dc.contributor.authorDiego A. S.; Pontespt_BR
dc.contributor.authorRodrigo M.; Gauzept_BR
dc.contributor.authorGisele F.; Rosapt_BR
dc.contributor.authorFernanda A.; Rittnerpt_BR
dc.contributor.authorRoberto; Bassopt_BR
dc.contributor.authorErnani A.pt_BR
unicamp.author.emaileabasso@uem.brpt_BR
unicamp.author[Rittner, Roberto] Univ Estadual Campinas, Inst Chem, Phys Organ Chem Lab, BR-13083970 Sao Paulo, Brazilpt_BR
unicamp.author.external[de Melo, Ulisses Zontapt
unicamp.author.externalSilva, Rai G. M.pt
unicamp.author.externalYamazaki, Diego A. S.pt
unicamp.author.externalPontes, Rodrigo M.pt
unicamp.author.externalGauze, Gisele F.pt
unicamp.author.externalRosa, Fernanda A.pt
unicamp.author.externalBasso, Ernani A.] Univ Estadual Maringa, Dept Chem, BR-87020900 Maringa, Parana, Brazilpt
dc.subjectDensity-functional Theorypt_BR
dc.subjectHydrogen-bondpt_BR
dc.subjectLactamspt_BR
dc.subjectMoleculespt_BR
dc.subjectBetapt_BR
dc.description.abstractThis study reports the results of ab initio and density functional theory (DFT) electronic structure calculations as well as (3)J(HH) experimental and calculated coupling constant data obtained in the investigation of the conformational equilibrium of 3-halo-derivatives of 1-methylpyrrolidin-2-one. The five-membered ring assumes an envelope conformation owing to the plane of formation of the O-C-N-R bond, with C4 forming the envelope lid. When the conformation changes, the lid alternates between positions above and below the amide plane. The a-carbonyl halogen assumes two positions: a pseudo-axial and a pseudo-equatorial. In the gaseous phase, the calculations indicate that the pseudo-axial conformer is more stable and preferable going down the halogen family. Natural bond orbital analysis showed that electronic delocalization is significant only for the iodo derivative. In the other derivatives, the electrostatic repulsion between oxygen and the halogen determines the conformational equilibrium. When the solvated molecule was taken into account, the pseudo-equatorial conformer population increased with the relative permittivity of the solvent. This variation was strong in the fluoro derivative, and the preference was inverted. In the chlorine derivative, the two populations became closer in methanol and acetonitrile. In the bromine and iodine derivatives, the percentage of pseudo-equatorial conformer increased only slightly owing to the dipole moment of the conformation: the pseudo-equatorial conformation has a greater dipole moment and thus is stable in media with high relative permittivity.en
dc.relation.ispartofJOURNAL OF PHYSICAL CHEMISTRY Apt_BR
dc.publisher.countryWASHINGTONpt_BR
dc.publisherAMER CHEMICAL SOCpt_BR
dc.date.issued2015-Marpt_BR
dc.identifier.citationNmr Spectroscopy And Theoretical Calculations In The Conformational Analysis Of 1-methylpyrrolidin-2-one 3-halo-derivatives. Amer Chemical Soc, v. 119, p. 2111-2121 Mar-2015.pt_BR
dc.language.isoenpt_BR
dc.description.volume119pt_BR
dc.description.issuenumber10pt_BR
dc.description.firstpage2111pt_BR
dc.description.lastpage2121pt_BR
dc.rightsfechadopt_BR
dc.sourceWOSpt_BR
dc.identifier.issn1089-5639pt_BR
dc.identifier.wosidWOS:000351188900031pt_BR
dc.identifier.doi10.1021/jp512378gpt_BR
dc.identifier.urlhttp://pubs.acs.org/doi/abs/10.1021/jp512378gpt_BR
dc.description.sponsorshipConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)pt_BR
dc.description.sponsorshipCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)pt_BR
dc.description.sponsorshipFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)pt_BR
dc.description.sponsorship1Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)pt_BR
dc.description.sponsorship1Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)pt_BR
dc.description.sponsorship1Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)pt_BR
dc.description.sponsordocumentnumberFAPESP [2012/03933-5]pt
dc.date.available2016-06-07T13:14:36Z-
dc.date.accessioned2016-06-07T13:14:36Z-
dc.description.provenanceMade available in DSpace on 2016-06-07T13:14:36Z (GMT). No. of bitstreams: 1 wos_000351188900031.pdf: 1811351 bytes, checksum: 663656d8cd133b0a25ff6f8a223fb1f5 (MD5) Previous issue date: 2015en
dc.identifier.urihttp://repositorio.unicamp.br/jspui/handle/REPOSIP/241674-
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