title: Dynamics and the Regiochemistry of Nitration of Toluene.
abstract: The regiochemistry of the nitration of toluene by NO2+BF4-in dichloromethane is accurately predicted from trajectories in explicit solvent. Simpler models and approaches based on transition state theory fail to account for the selectivity. Potential of mean force calculations find no free-energy barrier for reaction of the toluene/NO2+BF4-encounter complex, yet the trajectories require an extraordinary 3 ps to descend an exergonic slope. The selectivity is decided late in long trajectories because their completion requires solvent and counterion reorganization. The normal descriptive understanding of the regiochemistry based on transition-state energies is unsupported.
authors: Department of Chemistry, Texas A&M University , 3255 TAMU, College Station, Texas 77843, United States.
authors: Yexenia
authors: Y
authors: Nieves-Quinones
authors: Department of Chemistry, Texas A&M University , 3255 TAMU, College Station, Texas 77843, United States.
authors: Daniel A
authors: DA
authors: Singleton
mesh_terms: D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D009010:Monte Carlo Method; D009574:Nitro Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism; D014050:Toluene / Q000737:chemistry*
chemical_list: D009574:Nitro Compounds; D014050:Toluene