Conformational Analysis And Stereoelectronic Effects In Trans-1,2-dihalocyclohexanes: 1h Nmr And Theoretical Investigation

dc.creatorFreitas M.P.
dc.creatorRittner R.
dc.creatorTormena C.F.
dc.creatorAbraham R.J.
dc.date2005
dc.date2015-06-26T14:08:29Z
dc.date2015-11-26T14:08:21Z
dc.date2015-06-26T14:08:29Z
dc.date2015-11-26T14:08:21Z
dc.date.accessioned2018-03-28T21:08:56Z
dc.date.available2018-03-28T21:08:56Z
dc.identifier
dc.identifierSpectrochimica Acta - Part A: Molecular And Biomolecular Spectroscopy. , v. 61, n. 8, p. 1771 - 1776, 2005.
dc.identifier13861425
dc.identifier10.1016/j.saa.2004.07.007
dc.identifierhttp://www.scopus.com/inward/record.url?eid=2-s2.0-17844410384&partnerID=40&md5=1135dbe03b9671dd7d577e44f2bfe1da
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/93597
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/93597
dc.identifier2-s2.0-17844410384
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1240981
dc.descriptionThe conformational equilibrium of trans-1,2-difluoro- (1), trans-1,2-dichloro- (2) and trans-1,2-dibromo-cyclohexane (3) was studied through a combined method of NMR, theoretical calculations and solvation theory. The solvent dependence of the JH1,H23 NMR coupling constants together with theoretical calculations allow the direct determination of the conformational equilibria without recourse to model compounds. The coupling constants were obtained with the aid of spectrum simulation, since these symmetric molecules present complex coupling systems. The observed couplings, when analysed by solvation theory and utilising DFT geometries (B3LYP/6-311+G**), gave energy values of Eee - Eaa of 0.10, 0.95 and 1.40 kcal mol-1 in the vapour phase for 1, 2 and 3, respectively, decreasing to -0.63, 0.36 and 0.93 kcal mol-1 in CCl4 and to -1.91, -0.80 and -0.05 kcal mol-1 in DMSO solution. The diaxial preference for all compounds is explained by natural bond orbital (NBO) analysis, which shows important hyperconjugative effects in this conformation. The "gauche effect" for compounds with more electronegative substituents, which are in gauche arrangement in the ee conformation, also plays a relevant role in more polar solvents. © 2004 Elsevier B.V. All rights reserved.
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dc.languageen
dc.publisher
dc.relationSpectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
dc.rightsfechado
dc.sourceScopus
dc.titleConformational Analysis And Stereoelectronic Effects In Trans-1,2-dihalocyclohexanes: 1h Nmr And Theoretical Investigation
dc.typeArtículos de revistas


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