Solvent nucleophilicities of hexafluoroisopropanol/water mixtures
Solvent nucleophilicities of hexafluoroisopropanol/water mixtures
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DOI：
10.1002/poc.3064
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发表时间：
2013-01-01
影响因子：
1.8
通讯作者：
Mayr, Herbert
中科院分区：
文献类型：
--
作者：
Ammer, Johannes;Mayr, Herbert
采用激光闪光光解二苯甲基三芳基鏻盐的方法，测定了1，1，1，3，3，3-六氟-2-丙醇（HFIP）和水的混合溶剂中不同供体和受体取代的二苯甲基鎓离子在50 ~ 99%HFIP（w/w）范围内的捕获速率常数k1。从这些速率常数，我们推导出特定的溶剂反应性参数N1和SN HFIP/水的混合物定义的线性自由能关系lg k1（20摄氏度）？sN（N1+？E）。版权所有（C）2012约翰威利父子有限公司
First-order rate constants k1 for the trapping of various donor- and acceptor-substituted benzhydrylium ions in mixtures of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and water ranging from 50 to 99% HFIP (w/w) were determined by laser flash photolytic generation of benzhydrylium ions from benzhydryl triarylphosphonium salts in these solvents. From these rate constants, we derived the solvent-specific reactivity parameters N1 and sN for HFIP/water mixtures as defined by the linear free energy relationship lg k1(20 degrees C)?=?sN(N1?+?E). Copyright (C) 2012 John Wiley & Sons, Ltd.