The role of stereoelectronic interactions in the conformational isomerism of some phosphorus-containing model compounds

dc.creatorFreitas, MP
dc.creatorRittner, R
dc.creatorTormena, CF
dc.creatorAbraham, RJ
dc.date2008
dc.dateJUN
dc.date2014-11-16T06:50:35Z
dc.date2015-11-26T16:20:47Z
dc.date2014-11-16T06:50:35Z
dc.date2015-11-26T16:20:47Z
dc.date.accessioned2018-03-28T23:03:06Z
dc.date.available2018-03-28T23:03:06Z
dc.identifierJournal Of Physical Organic Chemistry. John Wiley & Sons Ltd, v. 21, n. 6, n. 505, n. 509, 2008.
dc.identifier0894-3230
dc.identifierWOS:000257090800010
dc.identifier10.1002/poc.1372
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/72403
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/72403
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/72403
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1267867
dc.descriptionThe rotational isomerism of model phosphorus-containing compounds was evaluated by using theoretical methodologies. The trans rotamer of chloromethylphosphonic acid dichloride (1) was found to be the prevailing form in the gas phase and in non-polar solvents, with an inverse behaviour from chloroform solution. Although the use of direct spin-spin coupling constants (SSCCs) do not apply for the quantitative determination of conformers in 1, due to the small dependence of J with conformation, the observed measurements and calculated individual couplings suggest that the gauche conformer is progressively stabilized with increasing the solvent polarity. In addition, theoretical calculations at the CBS-Q level for the corresponding phosphine of 1 (compound 2) showed the gauche rotamer as the prevailing one in the isolated state. Natural Bond Orbital (NBO) analysis indicated that steric and electrostatic effects rule the rotational isomerism of 1, while the anomeric effect n(P) -> sigma(CCl)* also plays an important role on the conformational equilibrium of 2. Copyright (C) 2008 John Wiley & Sons, Ltd.
dc.description21
dc.description6
dc.description505
dc.description509
dc.languageen
dc.publisherJohn Wiley & Sons Ltd
dc.publisherChichester
dc.publisherInglaterra
dc.relationJournal Of Physical Organic Chemistry
dc.relationJ. Phys. Org. Chem.
dc.rightsfechado
dc.rightshttp://olabout.wiley.com/WileyCDA/Section/id-406071.html
dc.sourceWeb of Science
dc.subjectconformational analysis
dc.subjectsolvation theory
dc.subjectphosphorus-containing compounds
dc.subjectclassical effects
dc.subjectanomeric effect
dc.subjectNmr
dc.subjectSolvation
dc.subjectChemistry
dc.subjectSpectra
dc.subjectAnalogs
dc.subjectIr
dc.titleThe role of stereoelectronic interactions in the conformational isomerism of some phosphorus-containing model compounds
dc.typeArtículos de revistas


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