Conformational and electronic interaction studies of 2-fluoro-substituted N,N-dimethylacetamides

dc.creatorOlivato, PR
dc.creatorGuerrero, SA
dc.creatorYreijo, MH
dc.creatorRittner, R
dc.creatorTormena, CF
dc.date2002
dc.dateAPR 24
dc.date2014-11-19T22:18:51Z
dc.date2015-11-26T17:08:55Z
dc.date2014-11-19T22:18:51Z
dc.date2015-11-26T17:08:55Z
dc.date.accessioned2018-03-28T23:57:35Z
dc.date.available2018-03-28T23:57:35Z
dc.identifierJournal Of Molecular Structure. Elsevier Science Bv, v. 607, n. 41700, n. 87, n. 99, 2002.
dc.identifier0022-2860
dc.identifierWOS:000174630100001
dc.identifier10.1016/S0022-2860(01)00761-X
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/56514
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/56514
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/56514
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1280498
dc.descriptionThe nu(CO) IR analysis of the 2-fluoro-substituted NN-dimethylacetamides RC(O)NMe2 [R=FCH2 (1), F2CH (2) and F3C (3)] and of the parent NN-dimethylacetatnide [R=CH3 (4)] in solvents of increasing polarity suggests the occurrence of Fermi resonance for 2, 3 and 4 and of cis-gauche rotational isomerism for 1. The 1st overtone analysis along with ab initio calculations at MP2/b - 31 + G(d,p) level are in agreement with the existence of the cis and gauche conformers for 1 and indicate the occurrence of cis-gauche and gauche-gauche conformers for 2 and of a single cis-gauche-gauche rotamer for 3. The stabilisation of the gauche rotamer with respect to the cis rotamer for 1 and of the gauche-gauche rotamer over the cis-gauche rotamer for 2, along with the unique cis-gauche-gauche rotamer for 3 is discussed in terms of a -I inductive effect of the CF12 group, a Repulsive Field Effect between the C=O and C - F dipoles and the orbital interaction between one or two fluorine 2p lone pairs (in the gauche conformation) and the pi(CO)* orbital. Eigenvector analysis shows that the fluorine 2p orbital coefficient at the LUMO increases progressively, going from the cis-gauche-gauche rotamer of 3 to the cis-gauche rotamer of 2, to the gauche-gauche rotamer of 2 and to the gauche rotamer of 1. Carbonyl frequency gauche shifts (Deltanu) are in line with this trend and support the pi(CO)*/n(rho) orbital increases in the same direction. (C) 2002 Elsevier Science B.V. All rights reserved.
dc.description607
dc.description41700
dc.description87
dc.description99
dc.languageen
dc.publisherElsevier Science Bv
dc.publisherAmsterdam
dc.publisherHolanda
dc.relationJournal Of Molecular Structure
dc.relationJ. Mol. Struct.
dc.rightsfechado
dc.rightshttp://www.elsevier.com/about/open-access/open-access-policies/article-posting-policy
dc.sourceWeb of Science
dc.subject2-fluoro-substituted N,N-dimethylacetamides
dc.subjectelectronic interactions
dc.subjectconformational analysis
dc.subjectinfrared spectroscopy
dc.subjecttheoretical calculations
dc.subjectSubstituted Carbonyl-compounds
dc.subjectSpectroscopy
dc.subjectSolvation
dc.subjectIsomerism
dc.subjectNmr
dc.titleConformational and electronic interaction studies of 2-fluoro-substituted N,N-dimethylacetamides
dc.typeArtículos de revistas


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