Please use this identifier to cite or link to this item: http://repositorio.unicamp.br/jspui/handle/REPOSIP/81847
Type: Artigo de periódico
Title: On the (4)J(HH) long-range coupling in 2-bromocyclohexanone: conformational insights
Author: Coelho, JV
Freitas, MP
Tormena, CF
Rittner, R
Abstract: 2-Bromocyclohexanone is a model compound in which a (4)J(H2,H6) coupling constant is observed, whereas the corresponding (4)J(H2,H4) is absent. The observed long-range coupling is not only a result of the known W-type coupling, in the axial conformation, but also because of the less usual diaxial spin-spin coupling in the equatorial conformer. The carbonyl group plays a determining role in describing the coupling pathway, as concluded by natural bond orbital (NBO) analysis; although the sigma(C2-H2) -> sigma(*) (C1(O)-C6) and sigma(C6-H6) -> sigma(*) (C1(O)-C2) interactions in the axial conformer contribute for transmitting the spin information associated with the W-type coupling, the strong sigma(C2-H2) -> pi(*) (C=0) and sigma(C6-H6) -> pi(*) (C=0) hyperconjugations in the equatorial conformer define an enhanced coupling pathway for (4)J(H2,H6), despite the inhibition of this coupling because of n(o) -> sigma(*) (C(O)-C) interaction and the large carbonyl angle. These findings provide the experimental evidence that orbital interactions contribute for the conformational isomerism of 2-bromocyclohexanone. Copyright (c) 2008 John Wiley & Sons, Ltd.
Subject: NMR
(4)J(HH)
2-bromocyclohexanone
carbonyl group
NBO
Country: EUA
Editor: Wiley-blackwell
Rights: fechado
Identifier DOI: 10.1002/mrc.2385
Date Issue: 2009
Appears in Collections:Unicamp - Artigos e Outros Documentos

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