Main-Group Metallomimetics: Transition Metal-like Photolytic CO Substitution at Boron

The carbon monoxide adduct of an unhindered and highly reactive CAAC-bound arylborylene, [(CAAC)B(CO)Ar] (CAAC = cyclic (alkyl) (amino)carbene), has been prepared using a transfer reaction from the linear iron borylene complex [(PMe3) (CO)(3)Fe=BAr]. [(CAAC)B(CO)Ar] is a source of the dicoordinate [(CAAC)ArB:] borylene that can be liberated by selective photolytic CO extrusion and that, although highly reactive, is sufficiently long-lived to react intermolecularly. Through trapping of the borylene generated in this manner, we present, among others, the first metal-free borylene(I) species containing a nitrogen-based donor, as well as a new boron-containing radical.