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

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

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)8185-8193
Number of pages9
JournalOrganic & biomolecular chemistry
Volume17
Issue number35
DOIs
Publication statusPublished - 21 Sep 2019

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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