Copper(I)−α-Ketocarboxylate Complexes:  Characterization and O₂ Reactions That Yield Copper−Oxygen Intermediates Capable of Hydroxylating Arenes

A series of copper(I)−α-ketocarboxylate complexes have been prepared and shown to exhibit variable coordination modes of the α-ketocarboxylate ligand. Reaction with O 2 induces decarboxylation of this ligand, and the derived copper−oxygen intermediate(s) has been intercepted, resulting in hydroxylation of an arene substituent on the supporting N-donor ligand. Theoretical calculations have provided intriguing mechanistic notions for the process, notably implicating hydroxylation pathways that involve novel [Cu I −OOC(O)R] and [Cu II −O -• ↔ Cu III O 2- ] + species.