The Mechanism of C–H Bond Oxidation by Aqueous Permanganate
| Autor: | Jens Blotevogel, Thomas Borch, Tom Sale, Arthur N. Mayeno, Anthony K. Rappé |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
chemistry.chemical_classification
Alkane Aqueous solution Chemistry Permanganate Water Oxides Alcohol General Chemistry 010501 environmental sciences Carbocation 010402 general chemistry Photochemistry 01 natural sciences Aldehyde 0104 chemical sciences Kinetics chemistry.chemical_compound Manganese Compounds Reagent Environmental Chemistry Carboxylate Oxidation-Reduction 0105 earth and related environmental sciences |
| Zdroj: | Environmental Science & Technology. 52:9845-9850 |
| ISSN: | 1520-5851 0013-936X |
| DOI: | 10.1021/acs.est.8b03157 |
| Popis: | The permanganate ion (MnO4–) has been widely used as a reagent for water treatment for over a century. It is a strong enough oxidant to activate carbon–hydrogen bonds, one of the most important reactions in biological and chemical systems. Our current textbook understanding of the oxidation mechanism in aqueous solution involves an initial, rate-limiting hydride abstraction by permanganate followed by reaction of the carbocation with bulk water to form an alcohol. This mechanism fits well into the classic oxidation sequence of alkane → alcohol → aldehyde → carboxylate, the central paradigm for both abiotic and biotic alkane oxidation in aqueous environments. In this study, we provide three lines of evidence through (1) a broken-symmetry density functional theory approach, (2) isotope labeling experiments, and (3) kinetic network modeling to demonstrate that aqueous permanganate can circumvent prior alcohol formation and produce aldehydes directly via a reaction path that bifurcates after the initial trans... |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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