ArticleJournal of the American Chemical Society2014
Mechanistic insights into the oxidation of substituted phenols via hydrogen atom abstraction by a cupric-superoxo complex.
Article in Journal of the American Chemical Society, 2014. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 48 papers.
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48 citing papers in PubMed, 145 citations in OpenAlex.
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- Generation and Aerobic Oxidative Catalysis of a Cu(II) Superoxo Complex Supported by a Redox-Active Ligand.Journal of the American Chemical Society · 2022Article
- An Iron(III) Superoxide Corrole from Iron(II) and Dioxygen.Angewandte Chemie (International ed. in English) · 2022Article
- Structural Elucidation, Aggregation, and Dynamic Behaviour ofEuropean journal of inorganic chemistry · 2021Article
- Reactivity Properties of Mixed- and High-Valent Bis(μ-Hydroxide)-Dinickel Complexes.ACS omega · 2021Article
- Proton-coupled electron transfer reactivities of electronically divergent heme superoxide intermediates: a kinetic, thermodynamic, and theoretical study.Chemical science · 2021Article
- Ligand-Constraint-Induced Peroxide Activation for Electrophilic Reactivity.Angewandte Chemie (International ed. in English) · 2021Article
- A Thioether-Ligated Cupric Superoxide Model with Hydrogen Atom Abstraction Reactivity.Journal of the American Chemical Society · 2021Article
- Characterization and reactivity study of non-heme high-valent iron-hydroxo complexes.Chemical science · 2021Article
- Hydroxyl Transfer to Carbon Radicals by Mn(OH) vs Fe(OH) Corrole Complexes.Inorganic chemistry · 2020Article
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Authors and funding
10 authors at 4 institutions in 2 countries.
Funding
Abstract
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. Significant deuterium kinetic isotope effects and a positive correlation of second-order rate constants (k2) 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) ln k2 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, (18)O-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 (18)O-labeled DTBQ and elimination of the R group.
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