Are one-step aromatic nucleophilic substitutions of non-activated benzenes concerted processes?

Luis R. Domingo, Mar Ríos-Gutiérrez, Eduardo Chamorro, Patricia Pérez

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

5 Citas (Scopus)

Resumen

Aromatic nucleophilic substitution (SNAr) reactions of non-electrophilically activated benzenes have been studied within the Molecular Electron Density Theory (MEDT) at the B3LYP/6-311+G(d) computational level. These reactions, taking place through a one-step mechanism, present a high activation Gibbs free energy, ΔG≠ = 31.0 kcal mol-1, which decreases to 22.1 kcal mol-1 in the intramolecular process. A topological analysis of the electron localisation function along the reaction paths permits establishing the non-concerted nature of these SNAr reactions. A series of unstable structures, with similar electronic structures to those of Meisenheimer intermediates, are characterised. The present MEDT study makes it possible to establish that even these one-step SNAr reactions involving only two single bonds are non-concerted processes.

Idioma originalInglés
Páginas (desde-hasta)8185-8193
Número de páginas9
PublicaciónOrganic & biomolecular chemistry
Volumen17
N.º35
DOI
EstadoPublicada - 21 sep 2019

Áreas temáticas de ASJC Scopus

  • Bioquímica
  • Química física y teórica
  • Química orgánica

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