Citation: ZHU Zunwei, YANG Qiaofeng, XU Zhenzhen, ZHAO Dongxia, FAN Hongjun, YANG Zhongzhi. Fukui Function and Local Softness Related to the Regioselectivity of Electrophilic Addition Reactions[J]. Acta Physico-Chimica Sinica, ;2018, 34(5): 519-527. doi: 10.3866/PKU.WHXB201710126 shu

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

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

Corresponding author: XU Zhenzhen, jane_xu@dicp.ac.cn ZHAO Dongxia, zhaodxchem@lnnu.edu.cn
Received Date: 30 August 2017
Revised Date: 21 September 2017
Accepted Date: 9 October 2017
Available Online: 12 May 2017
Fund Project: the National Natural Science Foundation of China 21483083, 21133005The project was supported by the National Natural Science Foundation of China (21483083, 21133005) and the Natural Science Foundation of Liaoning Province, China (2014020150)the National Natural Science Foundation of China 21483083the Natural Science Foundation of Liaoning Province, China 2014020150

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