Resumen
The hard and soft acids and bases principle is used together with the condensed fukui function to analyze the regioselectivity and reactivity of two model 1,3-dipolar cycloaddition reactions. Results obtained for benzonitrile oxide with vinyl p-nitrobenzoate or 1-acetyl vinyl p-nitrobenzoate illustrate the value of these concepts to describe their inherent reactivity. The calculations of the interaction energy by density functional theory using a perturbative, orbital independent method suggest the specific direction of the electronic process at each of the reaction sites. The electrophilic nature of the 1,3-dipole and the nucleophilic nature of the two dipolarophiles was determined by this model. The partitioning of the interaction energy in a term resulting from the chemical potential equalization principle at constant external potential and a term resulting from the maximum hardness principle at constant chemical potential show that the former term, arising from the charge-transfer process, contributes to a lesser extent than the term arising from the reshuffling of the charge distribution. The use of density functional theory concepts and the hard and soft acids and bases principle is a promising alternative to frontier orbital theory.
Idioma original | Inglés |
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Páginas (desde-hasta) | 6292-6296 |
Número de páginas | 5 |
Publicación | Journal of Physical Chemistry A |
Volumen | 102 |
N.º | 31 |
DOI | |
Estado | Publicada - 30 jul. 1998 |