Stable Thio‐, Seleno‐ and Telluro‐Aminyl Radicals Derived from Triplet Nitrene

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Abstract
Comprehensive Summary: Aminyl radicals of the type •NR₂, featuring a nitrogen‐centered unpaired electron, are highly reactive intermediates that are notoriously difficult to isolate in the condensed phase. Herein, we report the synthesis of thio‐, seleno‐ and telluro‐aminyl radicals 2 – 4 , obtained in one step from reactions of an isolable triplet nitrene with diphenyldichalcogenides. Radicals 3 and 4 represent the first stable examples of seleno‐ and telluro‐substituted aminyl radicals. Compounds 2 – 4 were characterized by single‐crystal X‐ray diffraction, electron paramagnetic resonance and UV/Vis absorption spectroscopy. This work not only expands the family of isolable nitrogen‐centered radicals, but also opens new avenues for main‐group radical chemistry involving heavier p‐block elements.
Funding Information
  • Basic and Applied Basic Research Foundation of Guangdong Province (SL2024A04J01805)
  • National Natural Science Foundation of China (22322112)
  • National Natural Science Foundation of China (22488101)

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