Artículo
Qualitative study of substituent effects on NMR15N and 17O chemical shifts
Contreras, Ruben Horacio
; Llorente, Tomás; Pagola, Gabriel Ignacio
; Bustamante Pilone, Manuel Guillermo; Pasqualini, Enrique E.; Melo, Juan Ignacio
; Tormena, Cláudio F.
Fecha de publicación:
08/2009
Editorial:
American Chemical Society
Revista:
Journal of Physical Chemistry A
ISSN:
1089-5639
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
A qualitative approach to analyze the electronic origin of substituent effects on the paramagnetic part of chemical shifts is described and applied to few model systems, where its potentiality can be appreciated. The formulation of this approach is based on the following grounds. The influence of different inter- or intramolecular interactions on a second-order property can be qualitatively predicted if it can be 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 orbitais that define some experimental trends of magnetic shielding constants. This approach is applied first to study the electronic origin of methyl-β substituent effects on both 15N and 17O chemical shifts, and afterward it is applied to a couple of examples of long-range substituent effects originated in charge transfer interactions such as the conjugative effect in aromatic compounds and σ-hyperconjugative interactions in saturated multicyclic compounds. © 2009 American Chemical Society.
Palabras clave:
1,3-Dithiane
,
Hyperconjugative Interactions
,
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Articulos(IFIBA)
Articulos de INST.DE FISICA DE BUENOS AIRES
Articulos de INST.DE FISICA DE BUENOS AIRES
Citación
Contreras, Ruben Horacio; Llorente, Tomás; Pagola, Gabriel Ignacio; Bustamante Pilone, Manuel Guillermo; Pasqualini, Enrique E.; et al.; Qualitative study of substituent effects on NMR15N and 17O chemical shifts; American Chemical Society; Journal of Physical Chemistry A; 113; 36; 8-2009; 9874-9880
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