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Updated: Jun 17, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Chalcogen σ-hole interaction enabled radical reactions
Yan Zhang1, Jin-Ru Chen1, Xiang-Yu Chen2,3
1School of Chemistry and Chemical Engineering, Shandong University of Technology, 266 West Xincun Road, Zibo 255049, China. qiangliu@sdut.edu.cn.
None:
Chalcogen bonding (ChB), an attractive noncovalent σ-hole interaction involving Group 16 elements, has recently emerged as a powerful activation mode in synthetic chemistry. This review provides a comprehensive overview of the burgeoning field of ChB enabled radical reactions, highlighting how these σ-hole interactions unlock unprecedented reactivities under mild, transition metal-free, and photocatalyst-free conditions. The discussion is structured around two principal mechanistic themes. The first section examines cationic ChB-enabled processes, wherein sulfonium and selenonium salts act as potent σ-hole donors to form photoactive charge-transfer complexes with Lewis bases or dichalcogenides. The second section explores neutral ChB-enabled radical reactions. Detailed mechanistic insights from spectroscopic, computational, and radical-trapping experiments underscore the critical role of ChB in orchestrating single-electron transfer. By consolidating these advances, this review illuminates the capabilities of chalcogen bonding as a tunable and versatile platform for radical generation and aims to inspire future developments in asymmetric catalysis, multicatalytic networks, and continuous-flow applications.
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