Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 22nd May 2019 from 11:00 AM to 1:00 PM (GMT).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.



σ-Holes promote the concertedness in nucleophilic aromatic substitution reactions of nitroarenes

Author affiliations

Abstract

The mechanism of the SNAr reactions between 1-halo-2,4-dinitrobenzenes and amines was revisited by means of DFT calculations. Remarkably and contrary to the traditional text-book perspective, the dehalogenation of 1-X-2,4-dinitrobenzenes bearing good leaving groups (X = Cl, Br and I) by soft nucleophiles involves a single-step mechanism passing through a barrierless C–X bond cleavage step. Solely the reaction of 1-fluoro-2,4-dinitrobenzene follows the traditional addition–elimination pathway. The analysis of the charge transfer patterns along the reaction path for the whole systems studied suggests that for those nitroarenes exhibiting σ-holes the dehalogenation mechanism occurs through a single-step. Nucleophile effects on the reaction rates were also discussed.

Graphical abstract: σ-Holes promote the concertedness in nucleophilic aromatic substitution reactions of nitroarenes

Back to tab navigation

Supplementary files

Publication details

The article was received on 21 Mar 2019, accepted on 24 Apr 2019 and first published on 26 Apr 2019


Article type: Paper
DOI: 10.1039/C9NJ01493D
New J. Chem., 2019, Advance Article

  •   Request permissions

    σ-Holes promote the concertedness in nucleophilic aromatic substitution reactions of nitroarenes

    S. Gallardo-Fuentes and R. Ormazábal-Toledo, New J. Chem., 2019, Advance Article , DOI: 10.1039/C9NJ01493D

Search articles by author

Spotlight

Advertisements