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Theoretically speaking: The mechanistic details associated with the generation and reaction of [CuO]+ species from CuI-α-ketocarboxylate complexes, especially with respect to modifications of the ligand supporting the copper center, were investigated (see scheme). Theoretical models were used to characterize the electronic structures of different [CuO]+ species and their reactivity in CH activation and O-atom transfer reactions. |
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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. |