Acta Phys. -Chim. Sin. ›› 2018, Vol. 34 ›› Issue (5): 519-527.doi: 10.3866/PKU.WHXB201710126

Special Issue: 密度泛函理论中的化学概念特刊

• ARTICLE • Previous Articles     Next Articles

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

Zunwei ZHU1,Qiaofeng YANG1,Zhenzhen XU1,2,*(),Dongxia ZHAO1,*(),Hongjun FAN2,Zhongzhi YANG1   

  1. 1 School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China
    2 Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, P. R. China
  • Received:2017-08-30 Published:2018-01-24
  • Contact: Zhenzhen XU,Dongxia ZHAO E-mail:jane_xu@dicp.ac.cn;zhaodxchem@lnnu.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21483083);the National Natural Science Foundation of China(21483083, 21133005);the Natural Science Foundation of Liaoning Province, China(2014020150)

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.

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

MSC2000: 

  • O641