Copper(I)-α-Ketocarboxylate Complexes: Characterization and O2 Reactions That Yield Copper-Oxygen Intermediates Capable of Hydroxylating Arenes
Hong, S.; Huber, S.; Gagliardi, L.; Cramer, C. J.; Tolman, W. B.
J. Am. Chem. Soc. 2007, 129, 14190.
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 O2 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 [CuI-OOC(O)R] and [CuII-O•- <--> CuIII=O2-]+ species.
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