An Anionic, Tetragonal Copper(II) Superoxide Complex

作者：Donoghue Patrick J; Gupta Aalo K; Boyce David W; Cramer Christopher J; Tolman William B^*

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

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(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.

• 出版日期2010-11-17