Abstract
We herein showcase the ability of NHC-coordinated dinuclear Ni(I) -Ni(I) complexes to override fundamental reactivity limits of mononuclear (NHC)Ni(0) catalysts in cross-couplings. This is demonstrated with the development of a chemoselective trifluoromethylselenolation of aryl iodides catalyzed by a Ni(I) dimer. A novel SeCF(3) -bridged Ni(I) dimer was isolated and shown to selectively react with Ar-I bonds. Our computational and experimental reactivity data suggest dinuclear Ni(I) catalysis to be operative. The corresponding Ni(0) species, on the other hand, suffers from preferred reaction with the product, ArSeCF(3) , over productive cross-coupling and is hence inactive.