Dication Diselenides as Reservoirs of Open-Shell Catalysts in Covalent Radical Catalysis

Abstract Chalcogenyl radicals are powerful catalysts for covalent radical catalysis (CoRC), enabling the design of efficient radical cascades that transform simple substrates into valuable molecular architectures. Among them, selenium-centered radicals exhibit particularly attractive reactivity profiles, yet their broader exploitation has been hampered by the limited availability of suitable precursors. Herein, we report a novel family of dicationic diselenides that act as readily activatable reservoirs of selenyl radicals. Their physicochemical properties are elucidated, and their catalytic competence in CoRC is demonstrated, establishing dicationic diselenides as a new platform for selenium-based radical catalysis.