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

doi:10.3866/PKU.WHXB201710126

Abstract

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 f^G(r), and generalized local softness s^G(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.

Key words: Fukui function, Local softness, Local hard-soft and acids-bases (HSAB) principle, Electrophilic addition reactions, Finite difference approximation, ABEEMσπ model

MSC2000:

O641

Zunwei ZHU,Qiaofeng YANG,Zhenzhen XU,Dongxia ZHAO,Hongjun FAN,Zhongzhi YANG. Fukui Function and Local Softness Related to the Regioselectivity of Electrophilic Addition Reactions[J].Acta Phys. -Chim. Sin., 2018, 34(5): 519-527.

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Fukui Function and Local Softness Related to the Regioselectivity of Electrophilic Addition Reactions

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