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

Gallardo-Fuentes S.; Ormazábal-Toledo R.

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 sigma-holes the dehalogenation mechanism occurs through a single-step. Nucleophile effects on the reaction rates were also discussed.

Más información

Título según WOS: sigma-Holes promote the concertedness in nucleophilic aromatic substitution reactions of nitroarenes
Título según SCOPUS: ?-Holes promote the concertedness in nucleophilic aromatic substitution reactions of nitroarenes
Título de la Revista: New Journal of Chemistry
Volumen: 43
Número: 20
Editorial: Royal Society of Chemistry
Fecha de publicación: 2019
Página de inicio: 7763
Página final: 7769
Idioma: English
DOI:

10.1039/c9nj01493d

Notas: ISI, SCOPUS