Lee JY1, Peterson RL, Ohkubo K, Garcia-Bosch I, Himes RA, Woertink J, Moore CD, Solomon EI, Fukuzumi S, Karlin KD.
J Am Chem Soc. 2014 Jul 16;136(28):9925-37. doi: 10.1021/ja503105b. Epub 2014 Jul 8.To obtain mechanistic insights into the inherent reactivity patterns for copper(I)-O2 adducts, a new cupric-superoxo complex [(DMM-tmpa)Cu(II)(O2(•-))](+) (2) [DMM-tmpa = tris((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)amine] has been synthesized and studied in phenol oxidation-oxygenation reactions. Compound 2 is characterized by UV-vis, resonance Raman, and EPR spectroscopies. Its reactions with a series of para-substituted 2,6-di-tert-butylphenols (p-X-DTBPs) afford 2,6-di-tert-butyl-1,4-benzoquinone (DTBQ) in up to 50% yields. Read More