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.
Jin et al. (Tue,) studied this question.