An anionic, tetragonal copper(II) superoxide complex |
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Authors: | Donoghue Patrick J Gupta Aalo K Boyce David W Cramer Christopher J Tolman William B |
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Institution: | Department of Chemistry, Supercomputing Institute, and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA. |
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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. |
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