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Type: Artigo de periódico
Title: The electronic origin of unusually large (n)J(FN) coupling constants in some fluoroximes
Author: Favaro, DC
Contreras, RH
Tormena, CF
Abstract: SOPPA(CCSD) calculations show that the FC term is the most important contribution to the through-space transmission of J(FN) coupling constants for the fluoroximes studied in this work. Because of the well-known behavior of FC term, a new rationalization for the experimental (TS)J(FN) SSCC is presented. It is mainly based on the overlapmatrix (S-ij) between fluorine and nitrogen lone pairs obtained from NBO analyses. An expression is proposed to take into account the influence of the electronic density (D-ij) between coupled nuclei as well as the s% character at the site of the coupling nuclei of bonds and non-bonding electron pairs involved in D-ij. In using this approach, a linear correlation between (TS)J(FN) versus D-ij is obtained. The most important aspect of this rationalization is related to the facility for understanding the behavior of some unusual experimental coupling constants. It is shown that, at least in this case, the electronic origin of the so-called through-space coupling is transmitted through to the overlap of orbitals on the coupled atoms, suggesting that, at least for these compounds, instead of through-space coupling, it should better be dubbed as 'through overlapping orbital coupling'. Copyright (C) 2013 John Wiley & Sons, Ltd.
Subject: (n)J(FN) through space coupling constants
overlap matrix
lone pairs interaction
d(FN) dependence
Country: EUA
Editor: Wiley-blackwell
Citation: Magnetic Resonance In Chemistry. Wiley-blackwell, v. 51, n. 6, n. 334, n. 338, 2013.
Rights: fechado
Identifier DOI: 10.1002/mrc.3950
Date Issue: 2013
Appears in Collections:Unicamp - Artigos e Outros Documentos

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