甲苯硝化的动力学和区域化学。
Dynamics and the Regiochemistry of Nitration of Toluene.
机构信息
Department of Chemistry, Texas A&M University , 3255 TAMU, College Station, Texas 77843, United States.
出版信息
J Am Chem Soc. 2016 Nov 23;138(46):15167-15176. doi: 10.1021/jacs.6b07328. Epub 2016 Nov 10.
Abstract
The regiochemistry of the nitration of toluene by NOBF 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/NOBF 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.
摘要
用显式溶剂中的轨迹准确预测了在二氯甲烷中用 NOBF 对甲苯的硝化作的区域化学。基于过渡态理论的更简单的模型和方法无法解释选择性。平均力势计算发现甲苯/NOBF 遭遇复合物反应没有自由能势垒，但轨迹需要非常长的 3 皮秒才能下降到非能垒的斜率。选择性是在长轨迹的后期决定的，因为它们的完成需要溶剂和抗衡离子的重组。基于过渡态能量的正常描述性理解对区域化学是不支持的。
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