Harnessing transient CAAC-stabilized mesitylborylenes for chalcogen activation

Newly synthesized adducts of CAAC-bound mesitylborylene with carbon monoxide (CO) and trimethylphosphine (PMe3) are established as efficient precursors for the in situ generation of the dicoordinate borylene [(CAAC)BMes] (CAAC = cyclic(alkyl)(amino)carbene), as demonstrated by their ability to activate elemental chalcogens. Upon thermal or photolytic activation, these precursors readily react with sulfur and selenium, yielding boron chalcogenides characterized by terminal boron–chalcogen double bonds. In contrast, the reaction with tellurium leads to the formation of an unusual diradical ditelluride species with a Te–Te bond. Quantum chemical calculations of its electronic structure indicate an open-shell singlet ground state characterized by significant diradical character. Further investigations into the redox behavior of these boron chalcogenides reveal intriguing transformations, including the redox-induced formation and cleavage of E–E bonds.