Heavy Halogen Atom Effect on C-13 NMR Chemical Shifts in Monohalo Derivatives of Cyclohexane and Pyran. Experimental and Theoretical Study

dc.creatorNeto, AC
dc.creatorDucati, LC
dc.creatorRittner, R
dc.creatorTormena, CF
dc.creatorContreras, RH
dc.creatorFrenking, G
dc.date2009
dc.dateSEP
dc.date2014-11-19T21:55:04Z
dc.date2015-11-26T16:30:13Z
dc.date2014-11-19T21:55:04Z
dc.date2015-11-26T16:30:13Z
dc.date.accessioned2018-03-28T23:11:15Z
dc.date.available2018-03-28T23:11:15Z
dc.identifierJournal Of Chemical Theory And Computation. Amer Chemical Soc, v. 5, n. 9, n. 2222, n. 2228, 2009.
dc.identifier1549-9618
dc.identifierWOS:000269488300006
dc.identifier10.1021/ct800520w
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/68196
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/68196
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/68196
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1269918
dc.descriptionFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.descriptionConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.descriptionAs 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 C-13 SCSs (substituent chemical shifts). This analysis led to the conclusion that compounds presenting strong hyperconjugative interactions involving the sigma(star)(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 C-13 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.
dc.description5
dc.description9
dc.description2222
dc.description2228
dc.descriptionFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.descriptionConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.descriptionCONICET [PIP 5119/05]
dc.descriptionUBATEC [X047]
dc.descriptionFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.descriptionConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.descriptionFAPESP [06/03990-2, 05159649-0, 06/02783-9]
dc.descriptionCONICET [PIP 5119/05]
dc.descriptionUBATEC [X047]
dc.languageen
dc.publisherAmer Chemical Soc
dc.publisherWashington
dc.publisherEUA
dc.relationJournal Of Chemical Theory And Computation
dc.relationJ. Chem. Theory Comput.
dc.rightsfechado
dc.sourceWeb of Science
dc.subjectNuclear-magnetic-resonance
dc.subjectDensity-functional Theory
dc.subjectCorrelated Molecular Calculations
dc.subjectSpin Coupling-constants
dc.subjectGaussian-basis Sets
dc.subjectShielding Tensors
dc.subjectDft
dc.titleHeavy Halogen Atom Effect on C-13 NMR Chemical Shifts in Monohalo Derivatives of Cyclohexane and Pyran. Experimental and Theoretical Study
dc.typeArtículos de revistas


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