Artículo
Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
Vilcachagua, Janaina Dantas; Ducati, Lucas C.; Rittner, Roberto; Contreras, Ruben Horacio
; Tormena, Cláudio F.
Fecha de publicación:
01/2011
Editorial:
American Chemical Society
Revista:
Journal of Physical Chemistry A
ISSN:
1089-5639
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of 1JCF NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH2; NO 2) is presented. The formulation of this approach is based on the influence of different conjugative and hyperconjugative interactions on a second-order property, which can be qualitatively predicted if it is known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitals, which define some experimental trends for 1JCF spin-spin coupling constants. In addition, DFT hybrid functionals were used, and a similar degree of confidence to compute the 1JCF with those observed for the SOPPA(CCSD) method was obtained. The 1JCF SSCCs for ezetimibe, a commercially fluorinated drug used to reduce cholesterol levels, were measured and DFT-calculated, and the qualitative approach quoted above was applied. As a byproduct, a possible method to determine experimentally a significant PSO contribution to 1JCF SSCCs is discussed. © 2011 American Chemical Society.
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Articulos(IFIBA)
Articulos de INST.DE FISICA DE BUENOS AIRES
Articulos de INST.DE FISICA DE BUENOS AIRES
Citación
Vilcachagua, Janaina Dantas; Ducati, Lucas C.; Rittner, Roberto; Contreras, Ruben Horacio; Tormena, Cláudio F.; Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives; American Chemical Society; Journal of Physical Chemistry A; 115; 7; 1-2011; 1272-1279
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