Solvent effects and mechanism for a nucleophilic aromatic substitution from QM/MM simulations.
The nucleophilic aromatic substitution (SNAr) reaction between azide ion and 4-fluoronitrobenzene has been investigated using QM/MM and DFT/PCM calculations in protic and dipolar aprotic solvents. The effects of solvation on the transition structures, the intermediate Meisenheimer complex, and the rate of reaction are elucidated. The large rate increases in proceeding from protic to dipolar aprotic solvents are only reproduced by the QM/MM methodology.
Acevedo
Orlando
O
Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06520-8107, USA.
Jorgensen
William L
WL
D001386:Azides / Q000737:chemistry*; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003198:Computer Simulation; D015394:Molecular Structure; D009578:Nitrobenzenes / Q000737:chemistry*; D012997:Solvents; D013816:Thermodynamics
D001386:Azides; D009578:Nitrobenzenes; D012997:Solvents