Lone-pair orientation effect of an alpha-oxygen atom on (1)J(CC) NMR spin-spin coupling constants in o-substituted phenols. Experimental and DFT study

dc.creatorTaurian, OE
dc.creatorContreras, RH
dc.creatorDe Kowalewski, DG
dc.creatorPerez, JE
dc.creatorTormena, CF
dc.date2007
dc.dateJUL-AUG
dc.date2014-11-14T06:17:32Z
dc.date2015-11-26T16:04:55Z
dc.date2014-11-14T06:17:32Z
dc.date2015-11-26T16:04:55Z
dc.date.accessioned2018-03-28T22:54:01Z
dc.date.available2018-03-28T22:54:01Z
dc.identifierJournal Of Chemical Theory And Computation. Amer Chemical Soc, v. 3, n. 4, n. 1284, n. 1294, 2007.
dc.identifier1549-9618
dc.identifierWOS:000247893400006
dc.identifier10.1021/ct7000396
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/81300
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/81300
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/81300
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1265603
dc.descriptionThe well-known N lone-pair orientation effect on (1)J(CC) spin-spin coupling constants (SSCCs) in oximes and their derivatives was used to study how negative hyperconjugative interactions of type LP1(O) -> sigma* CC depend on ortho interactions involving the OH group. This study demanded the following analyses: (i) a qualitative estimation of how (1)J(CC) SSCCs are affected by hyperconjugative interactions, ( ii) a study of similar stereochemical effects to those in oximes, but in (1)J(C1C2) and (1)J(C1C6) in a series of 2-substituted phenols, and ( iii) a quantitative estimation, with the natural bond order approach, of some key electron delocalization interactions. A few unexpected results are quoted. LP1(O) -> sigma* cc interactions are affected by proximity interactions as follows: ( a) they are enhanced by hydrogen bonds transferring charge into the (O-H)* antibonding orbital; (b) they are enhanced by proximity interactions of type LP1(O)center dot center dot center dot H-C; (c) they are inhibited by interactions of type LP(O-1)center dot center dot center dot H-O. Consequences of these observations are discussed.
dc.description3
dc.description4
dc.description1284
dc.description1294
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.subjectPolarization Propagator Analysis
dc.subjectOne-bond
dc.subjectConfigurational Assignment
dc.subjectNonempirical Calculations
dc.subjectConformational-analysis
dc.subjectDensity
dc.subjectTransmission
dc.subjectExchange
dc.subjectConjugation
dc.subjectDerivatives
dc.titleLone-pair orientation effect of an alpha-oxygen atom on (1)J(CC) NMR spin-spin coupling constants in o-substituted phenols. Experimental and DFT study
dc.typeArtículos de revistas


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