期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 136, 期 28, 页码 9925-9937出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja503105b
关键词
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资金
- NIH [DK31450, GM28962]
- JSPS [20108010, 23750014, 26620154, 26288037]
- JST (ALCA)
- Grants-in-Aid for Scientific Research [26620154, 26288037] Funding Source: KAKEN
To obtain mechanistic insights into the inherent reactivity patterns for copper(I)-O-2 adducts, a new cupric superoxo complex [(DMM-tmpa)Cu11(O-2(center dot-))](+) (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. Significant deuterium kinetic isotope effects and a positive correlation of second-order rate constants (k(2)) compared to rate constants for p-X-DTBPs plus cumylperoxyl radical reactions indicate a mechanism that involves rate-limiting hydrogen atom transfer (HAT). A weak correlation of (k(B)T/e) In k(2) versus E-ox of p-X-DTBP indicates that the HAT reactions proceed via a partial transfer of charge rather than a complete transfer of charge in the electron transfer/proton transfer pathway. Product analyses, O-18-labeling experiments, and separate reactivity employing the 2,4,6-tri-tert-butylphenoxyl radical provide further mechanistic insights. After initial HAT, a second molar equiv of 2 couples to the phenoxyl radical initially formed, giving a Cu-II-OO-(ArO') intermediate, which proceeds in the case of p-OR-DTBP substrates via a two-electron oxidation reaction involving hydrolysis steps which liberate H2O2 and the corresponding alcohol. By contrast, four-electron oxygenation (O-O cleavage) mainly occurs for p-R-DTBP which gives O-18-labeled DTBQ and elimination of the R group.
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