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American Chemical Society, Journal of the American Chemical Society, 45(132), p. 15869-15871, 2010

DOI: 10.1021/ja106244k

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An Anionic, Tetragonal Copper(II) Superoxide Complex

Journal article published in 2010 by Patrick J. Donoghue, Aalo K. Gupta, David W. Boyce, Christopher J. Cramer ORCID, William B. Tolman
This paper is available in a repository.
This paper is available in a repository.

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Abstract

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(CH(3)CN)]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.