Acevedo Orlando, Jorgensen William L
Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06520-8107, USA.
Org Lett. 2004 Aug 19;6(17):2881-4. doi: 10.1021/ol049121k.
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.
利用量子力学/分子力学（QM/MM）和密度泛函理论/极化连续介质模型（DFT/PCM）计算方法，研究了叠氮离子与4-氟硝基苯之间在质子性溶剂和偶极非质子性溶剂中的亲核芳香取代（SNAr）反应。阐明了溶剂化对过渡结构、中间体迈森海默络合物以及反应速率的影响。只有通过QM/MM方法才能重现从质子性溶剂到偶极非质子性溶剂时反应速率的大幅增加。
