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Updated: Nov 8, 2025

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Persistent 2c-3e σ-bonded heteronuclear radical cations centered on S/Se and P/As atoms
Wenbang Yang1, Wenqing Wang2, Leran Zhang3
1State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China. xpwang@nju.edu.cn.
Abstract:
The two-center three-electron (2c-3e) bonded species are important in chemical and biological science. Reported isolable 2c-3e σ-bonded species are usually constructed in homoatomic radicals. The one-electron oxidation of main-group heteronuclear species Nap(SPh)(P(Mes)2) (1), Nap(SePh)(P(Mes)2) (2), Nap(SPh)(As(Mes)2) (3) and Nap(SePh)(As(Mes)2) (4) produced persistent radical cations 1˙+-4˙+ in solution. Large couplings of heteroatoms in EPR spectra of 1˙+-4˙+, shorter bond distances and bigger Wiberg bond orders of Ch-Pn in 1˙+-4˙+ than those in 1-4 in DFT calculations indicate large amounts of spin densities over heteroatoms and the formation of 2c-3e σ-bonds between chalcogen and pnicogen atoms. This work provides evidence of 2c-3e σ-bonds constructed between main-group heteronuclears and rare examples of radical cations involving three-electron σ-bonds between S/Se and P/As atoms.
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