Definition of a nucleophilicity scale

Paula Jaramillo, Patricia Pérez, Renato Contreras, William Tiznado, Patricio Fuentealba

Resultado de la investigación: Article

95 Citas (Scopus)

Resumen

This work deals with exploring some empirical scales of nucleophilicity. We have started evaluating the experimental indices of nucleophilicity proposed by Legon and Millen on the basis of the measure of the force constants derived from vibrational frequencies using a probe dipole H-X (X = F,CN). The correlation among some theoretical parameters with this experimental scale has been evaluated, The theoretical parameters have been chosen as the minimum of the electrostatic potential Vmin, the binding energy (BE) between the nucleophile and the H-X dipole, and the electrostatic potential measured at the position of the hydrogen atom VH when the complex nucleophile and dipole H-X is in the equilibrium geometry. All of them present good correlations with the experimental nucleophilicity scale. In addition, the BEs of the nucleophiles with two other Lewis acids (one hard, BF3, and the other soft, BH3) have been evaluated. The results suggest that the Legon and Millen nucleophilicity scale and the electrostatic potential derived scales can describe in good approximation the reactivity order of the nucleophiles only when the interactions with a probe electrophile is of the hard-hard type. For a covalent interaction that is orbital controlled, a new nucleophilicity index using information of the frontier orbitals of both, the nucleophile and the electrophile has been proposed.

Idioma originalEnglish
Páginas (desde-hasta)8181-8187
Número de páginas7
PublicaciónJournal of Physical Chemistry A
Volumen110
N.º26
DOI
EstadoPublished - 6 jul 2006

Huella dactilar

Nucleophiles
nucleophiles
Electrostatics
electrostatics
dipoles
orbitals
Lewis Acids
probes
Vibrational spectra
Binding energy
Hydrogen
hydrogen atoms
reactivity
binding energy
interactions
Atoms
acids
Geometry
geometry
approximation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Citar esto

Jaramillo, Paula ; Pérez, Patricia ; Contreras, Renato ; Tiznado, William ; Fuentealba, Patricio. / Definition of a nucleophilicity scale. En: Journal of Physical Chemistry A. 2006 ; Vol. 110, N.º 26. pp. 8181-8187.
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Jaramillo, P, Pérez, P, Contreras, R, Tiznado, W & Fuentealba, P 2006, 'Definition of a nucleophilicity scale', Journal of Physical Chemistry A, vol. 110, n.º 26, pp. 8181-8187. https://doi.org/10.1021/jp057351q

Definition of a nucleophilicity scale. / Jaramillo, Paula; Pérez, Patricia; Contreras, Renato; Tiznado, William; Fuentealba, Patricio.

En: Journal of Physical Chemistry A, Vol. 110, N.º 26, 06.07.2006, p. 8181-8187.

Resultado de la investigación: Article

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