Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (10): 3892-3902.DOI: 10.6023/cjoc202106018 Previous Articles     Next Articles

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自由基的热力学和动力学定量参数

黄谋新a, 贾宗宾b,c, 罗三中a,b,c,*(), 程津培a,d,*()   

  1. a 清华大学化学系 基础分子科学中心 北京 100084
    b 中国科学院化学研究所 分子识别与功能重点实验室 北京 100190
    c 中国科学院大学 北京 100490
    d 南开大学化学学院 元素有机化学国家重点实验室 天津 300071
  • 收稿日期:2021-06-08 修回日期:2021-06-27 发布日期:2021-07-12
  • 通讯作者: 罗三中, 程津培
  • 作者简介:
    † 共同第一作者
  • 基金资助:
    国家自然科学基金(21672217); 国家自然科学基金(21861132003); 国家自然科学基金(22031006)

Quantitative Thermodynamic and Kinetic Parameters of Radical

Mouxin Huanga, Zongbin Jiab,c, Sanzhong Luoa,b,c(), Jin-Pei Chenga,d()   

  1. a Center for Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084
    b Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190
    c University of Chinese Academy of Sciences, Beijing 100490
    d State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071
  • Received:2021-06-08 Revised:2021-06-27 Published:2021-07-12
  • Contact: Sanzhong Luo, Jin-Pei Cheng
  • About author:
    † These authors contributed equally to this work.
  • Supported by:
    National Natural Science Foundation of China(21672217); National Natural Science Foundation of China(21861132003); National Natural Science Foundation of China(22031006)

Radical chemistry has gained its renaissence in the past decade and trendendous progresses have been witnessed in synthetic and material chemistry. However, mechanism studies are largely lagging behind comparing with rapid paces in the development of synthetic methodologies. On the other hand, the study of radical species remains a central theme in physial organic chemistry, and a large amount of thermodynamic and kinetic data on radicals have been generated over a century's reserch. Unfortuately, there has been no systematic compilation and curation of these quatitative data that are dispersedly distributed and buried in literature. As a result, most synthetic chemists are not acquainted with these valuable data. In this review, we aim in compiling and curating thermodynamic and kinetic parameters of radicals, that may hopefully provide a quantitative data basis for rational development and evolution of radical chemistry. The key parameters include radical stability energy (RSE), radical lifetime (τ), substituent constant (σ) and electrophilic index (ω). Fundamental concepts such as radical stability, Class S/O radical substitution effect, persistent/transient radical effect will be discussed on the basis of data.

Key words: radical property, quantitative parameters, stability, substituent effect, persistent radical effect