Dynamics of a gas-phase SNAr reaction: non-concerted mechanism despite the Meisenheimer complex being a transition state.

Abstract

The commonly accepted mechanism of the nucleophilic aromatic substitution (SNAr) reaction has been found to be governed by the nature of the Meisenheimer structure on the potential energy surface. A stable Meisenheimer intermediate favors a stepwise mechanism, while a Meisenheimer transition state favors a concerted mechanism. Here, we show by using a detailed potential energy map (using the DFT and DLPNO-CCSD(T)/CBS methods) and ab initio classical trajectory simulations that the F- + C6H5NO2 SNAr reaction involves a Meisenheimer transition state and follows a stepwise mechanism in contrast to the expected concerted pathway. The stepwise mechanism observed in the trajectory simulations takes place by the formation of various ion-dipole and σ-complexes. While the majority of the trajectories follow the multi-step mechanism and avoid the minimum energy path, a considerable fraction exhibit a roaming atom mechanism where the F atom hovers around the phenyl ring before the formation of the products.