Quantitative Thermodynamic and Kinetic Parameters of Radical

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 (tau), substituent constant (sigma) and electrophilic index (omega). Fundamental concepts such as radical stability, Class S/O radical substitution effect, persistent/transient radical effect will be discussed on the basis of data.

Automated summary

Radical chemistry has seen significant progress in the past decade, but mechanism studies are lacking compared to developments in synthetic methodologies. The study of radical species remains a central theme in physial organic chemistry, but there is a lack of systematic compilation and curation of quantitative data on radicals. This review aims to compile and curate thermodynamic and kinetic parameters of radicals to provide a quantitative data basis for the rational development and evolution of radical chemistry.