Quantitative Thermodynamic and Kinetic Parameters of Radical

Abstract

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.

Visible-Light-Induced Acylative Pyridylation of Styrenes

“…Besides its oceanic application in polar reactions, the Hammett analysis has also been widely used in the area of radical chemistry . In particular, Jiang et al have made significant contributions through their dual-parameter correlation analysis of radical reactions by introducing the polar substituent constant (σ mb ) and spin-delocalization substituent constant (σ jj· ) .…”