An Anionic, Tetragonal Copper(II) Superoxide Complex

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• 作者：Patrick J. Donoghue ; Aalo K. Gupta ; David W. Boyce ; Christopher J. Cramer ; William B. Tolman
• 刊名：Journal of the American Chemical Society
• 出版年：2010
• 出版时间：November 17, 2010
• 年：2010
• 卷：132
• 期：45
• 页码：15869-15871
• 全文大小：167K
• 年卷期：v.132,no.45(November 17, 2010)
• ISSN：1520-5126

文摘

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.