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An Anionic, Tetragonal Copper(II) Superoxide Complex

Donoghue, P. J.; Gupta, A. K.; Boyce, D. W.; Cramer, C. J.; Tolman, W. B.
J. Am. Chem. Soc. 2010, 132, 15869 (doi:10.1021/ja106244k)

Insight into copper-oxygen species proposed as intermediates in oxidation catalysis is provided by the identification of a Cu(II)-superoxide complex supported by a sterically hindered, pyridinedicarboxamide ligand. A tetragonal, end-on superoxide structure is proposed based on DFT calculations and UV-vis, NMR, EPR, and resonance Raman spectroscopy. The complex yields a trans-1,2-peroxodicopper(II) species upon reaction with [(tmpa)Cu(CH3CN)]OTf, and, unlike other known Cu(II)-superoxide complexes, acts as a base rather than an electrophilic (H-atom abstracting) reagent in reactions with phenols.