Pliego Josefredo R
Departamento de Ciencias Exatas e da Terra, Universidade Federal de Sao Paulo, 09972-270 Diadema, SP, Brazil.
J Phys Chem B. 2009 Jan 15;113(2):505-10. doi: 10.1021/jp808581t.
This article presents a detailed discussion on medium effect on ionic S(N)2 reactions. Ion pairing and the first solvation shell play the main role on reactivity. Ab initio calculations are used to show that a combination of apolar molecular cavity with polar hydroxyl groups can have catalytic effects on these reactions. The present results open an avenue of development for supramolecular catalysts able to control bimolecular ionic reactions. In particular, this new catalytic concept could be useful in nucleophilic fluorinations.
本文详细讨论了介质对离子型S(N)2反应的影响。离子对和第一溶剂化层对反应活性起主要作用。从头算计算表明，具有极性羟基的非极性分子腔组合可对这些反应产生催化作用。目前的结果为能够控制双分子离子反应的超分子催化剂开辟了一条发展途径。特别是，这种新的催化概念可能在亲核氟化反应中有用。
