Ab initio Study of Nucleophilic Aromatic Substitution of Polyfluorobenzene

Abstract

Calculations at ab initio levels of theory of the nucleophilic aromatic substitution of pentafluoronitrobenzene with amines demonstrate an addition–elimination mechanism (S_NAr), with the rate-determining step at the second transition state involving C–F bond breaking, and support the ortho-selectivity of the reactions based on the stability of the second transition states.