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

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.