摘要/Abstract

近十余年来, 自由基化学重新焕发了生机, 在合成化学和材料科学等领域取得了突破性的进展. 与突飞猛进的合成方法学研究相比, 人们对自由基反应的机制以及规律的研究和总结相对滞后. 另一方面, 自由基一直是物理有机化学领域重要的研究对象, 在横跨一个世纪的研究历程中积累了大量热力学和动力学参数, 但这些数据大多数都淹没在文献中, 缺乏系统的汇编和整理, 从而不被大多数合成化学家所熟知. 本综述拟对自由基热力学和动力学定量参数进行系统的汇编和整理, 以期为相关领域的理性设计与发展提供支撑数据. 这些数据参数主要包括自由基稳定化能(RSE)、自由基寿命(τ)、取代基常数(σ)、亲电性指数(ω)等. 以这些数据为基础, 将梳理一些重要的自由基化学基本概念如自由基稳定性、Class S/O自由基取代基效应、稳态和瞬态自由基效应等
关键词: 自由基性质, 定量参数, 稳定性, 取代基效应, 稳态自由基效应
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


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