物理化学学报2018，Vol.34Issue(5)：519-527,9.DOI:10.3866/PKU.WHXB201710126
Fukui函数和局域软度应用于亲电加成反应的区位选择性的研究
Fukui Function and Local Softness Related to the Regioselectivity of Electrophilic Addition Reactions
摘要
Abstract
Regioselectivities of electrophilic addition reactions of hydrogen chloride to asymmetric alkenes and benzeneselenenyl bromide to substituted styrenes have been investigated by using reactivity descriptors,including Fukui function f(r),local softness s(r),generalized Fukui function fG(r),and generalized local softness sG(r).All of them are obtained from the finite difference approximation method calculated by ab initio method at MP2/6-311++G(d,p) level of theory and our ABEEMσπ model,respectively.According to the generalized version of the local hard-soft and acid-base (HSAB) principle,the forecasted regioselectivities of our investigated additions using the ABEEMσπ model are in fair agreement with the experimental values.In particular,we can also rationalize their reaction rate constants by the generalized local softness,i.e.,the softest the site is,the easiest the reaction is.Hence,the generalized reactivity descriptors work quite well.关键词
Fukui函数/局域软度/局域硬-软酸碱原理/亲点加成反应/有限差分近似/ABEEMσπ模型Key words
Fukui function/Local softness/Local hard-soft and acids-bases (HSAB) principle/Electrophilic addition reactions/Finite difference approximation/ABEEMσπ model分类
化学化工引用本文复制引用
朱尊伟,杨巧凤,徐珍珍,赵东霞,樊红军,杨忠志..Fukui函数和局域软度应用于亲电加成反应的区位选择性的研究[J].物理化学学报,2018,34(5):519-527,9.基金项目
The project was supported by the National Natural Science Foundation of China (21483083,21133005) and the Natural Science Foundation of Liaoning Province,China (2014020150).国家自然科学基金(21483083,21133005)和辽宁省自然科学基金(2014020150)资助项目 （21483083,21133005）
