Empirical energy - Density relationships for the analysis of substituent effects in chemical reactivity

P. Pérez, Y. Simón-Manso, A. Aizman, P. Fuentealba, R. Contreras

Resultado de la investigación: Article

91 Citas (Scopus)

Resumen

Electronic substituent effects may be rationalized in terms of Hammett- like linear relationships between global energy-dependent quantities and local electronic descriptors of reactivity. These linear relationships are framed on a local hard and soft acids and bases (HSAB) principle in accord with previous results reported by Li and Evans [J. Am. Chem. Soc. 1995, 117, 7756]. Chemical substitution is indirectly assessed as local responses at the active center of the substrate, with the Fukui function and local softness as the key quantities within the present approach. This model of chemical substitution has a potential advantage with respect to models based on group properties using the electronegativity equalization principle (EEP), since the transferability of group properties is not required. The formalism is illustrated for the gas-phase basicity of alkylamines, and the gas-phase acidity of alkyl alcohols and alkyl thioalcohols. Our results based on the local HSAB rule agree well with those obtained from group properties analysis based on the EEP, suggesting that both empirical rules consistently complement each other.

Idioma originalEnglish
Páginas (desde-hasta)4756-4762
Número de páginas7
PublicaciónJournal of the American Chemical Society
Volumen122
N.º19
DOI
EstadoPublished - 17 may 2000

Huella dactilar

Electronegativity
Chemical reactivity
Substitution reactions
Gases
Chemical Models
Acids
Alkalinity
Acidity
Alcohols
Substrates

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Citar esto

Pérez, P. ; Simón-Manso, Y. ; Aizman, A. ; Fuentealba, P. ; Contreras, R. / Empirical energy - Density relationships for the analysis of substituent effects in chemical reactivity. En: Journal of the American Chemical Society. 2000 ; Vol. 122, N.º 19. pp. 4756-4762.
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Empirical energy - Density relationships for the analysis of substituent effects in chemical reactivity. / Pérez, P.; Simón-Manso, Y.; Aizman, A.; Fuentealba, P.; Contreras, R.

En: Journal of the American Chemical Society, Vol. 122, N.º 19, 17.05.2000, p. 4756-4762.

Resultado de la investigación: Article

TY - JOUR

T1 - Empirical energy - Density relationships for the analysis of substituent effects in chemical reactivity

AU - Pérez, P.

AU - Simón-Manso, Y.

AU - Aizman, A.

AU - Fuentealba, P.

AU - Contreras, R.

PY - 2000/5/17

Y1 - 2000/5/17

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