Dynamics and the Regiochemistry of Nitration of Toluene. Academic Article

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

• Singleton, Daniel

altmetric score

• 29.16

author list (cited authors)

• Nieves-Quinones, Y., & Singleton, D. A

citation count

• 55

complete list of authors

• Nieves-Quinones, Yexenia||Singleton, Daniel A

publication date

• January 2016

publisher

• American Chemical Society (ACS)  Publisher

published in

• Journal of the American Chemical Society  Journal

keywords

• Molecular Dynamics Simulation
• Molecular Structure
• Monte Carlo Method
• Nitro Compounds
• Quantum Theory
• Stereoisomerism
• Toluene

PubMed Central ID

• 27794598

Digital Object Identifier (DOI)

• 10.1021/jacs.6b07328

start page

• 15167

end page

• 15176

volume

• 138

issue

• 46

URL

• http%3A%2F%2Fdx.doi.org%2F10.1021%2Fjacs.6b07328