Anomeric effect on geminal and vicinal J(HH) NMR coupling constants

dc.creatorTormena, CF
dc.creatorRittner, R
dc.creatorContreras, RH
dc.creatorPeralta, JE
dc.date2004
dc.dateSEP 23
dc.date2014-11-15T19:35:38Z
dc.date2015-11-26T16:13:40Z
dc.date2014-11-15T19:35:38Z
dc.date2015-11-26T16:13:40Z
dc.date.accessioned2018-03-28T23:01:11Z
dc.date.available2018-03-28T23:01:11Z
dc.identifierJournal Of Physical Chemistry A. Amer Chemical Soc, v. 108, n. 38, n. 7762, n. 7768, 2004.
dc.identifier1089-5639
dc.identifierWOS:000223922100018
dc.identifier10.1021/jp047226z
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/77618
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/77618
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/77618
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1267391
dc.descriptionTrends for geminal ((2)J(HH)) and vicinal ((3)J(HH)) nuclear magnetic resonance indirect spin-spin coupling constants, SSCCs, for 2-methylthiirane (5) and 2-methyloxirane (6) are studied both from experimental and theoretical points of view to determine the influence of hyperconjugative interactions on these couplings. These two analogous compounds were chosen because it was expected that they exhibit quite different anomeric effects. Hyperconjugative interactions are investigated using the 'natural bond orbital' method. Coupling constants are calculated within the density functional theory including all four scalar contributions, that is, the Fermi contact, the spin-dipolar, and the paramagnetic and diamagnetic spin-orbital contributions. Solvent dielectric effects are taken into account using Tomasi's polarizable continuum model. Results for geminal couplings are consistent with linear correlations connecting (2)J(HH) with the coupling pathway occupation numbers taken from the literature. The present analysis suggests that both (2)J(HH) and (2)J(HH) coupling constants are sensitive probes to gauge the anomeric effect, as well as other hyperconjugative interactions.
dc.description108
dc.description38
dc.description7762
dc.description7768
dc.languageen
dc.publisherAmer Chemical Soc
dc.publisherWashington
dc.publisherEUA
dc.relationJournal Of Physical Chemistry A
dc.relationJ. Phys. Chem. A
dc.rightsfechado
dc.sourceWeb of Science
dc.subjectDensity-functional Theory
dc.subjectConformational-analysis
dc.subjectNegative Hyperconjugation
dc.subjectMolecular-structure
dc.subjectKarplus Equation
dc.subjectDouble Resonance
dc.subjectRelative Signs
dc.subjectBond Lengths
dc.subjectSolvation
dc.subjectCyclohexane
dc.titleAnomeric effect on geminal and vicinal J(HH) NMR coupling constants
dc.typeArtículos de revistas


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