Divergent Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0) Enables Chemoselective Trifluoromethylselenolation

We herein showcase the ability of NHC-coordinated dinuclear Ni^I -Ni^I complexes to override fundamental reactivity limits of mononuclear (NHC)Ni⁰ 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 SeCF₃ -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 Ni⁰ species, on the other hand, suffers from preferred reaction with the product, ArSeCF₃ , over productive cross-coupling and is hence inactive.