An anionic, tetragonal copper(II) superoxide complex.
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.
Department of Chemistry, Supercomputing Institute, and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA.
Patrick J
PJ
Donoghue
Aalo K
AK
Gupta
David W
DW
Boyce
Christopher J
CJ
Cramer
William B
WB
Tolman
D000838:Anions / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D015394:Molecular Structure; D013057:Spectrum Analysis; D013481:Superoxides / Q000737:chemistry*
D000838:Anions; D013481:Superoxides; D003300:Copper