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- Title
Electrochemical Activation of C−C Bonds through Mediated Hydrogen Atom Transfer Reactions.
- Authors
Yan, Bing; Shi, Changxia; Beckham, Gregg T.; Chen, Eugene Y.‐X.; Román‐Leshkov, Yuriy
- Abstract
Activating inert sp3–sp3 carbon‐carbon (C−C) bonds remains a major bottleneck in the chemical upcycling of recalcitrant polyolefin waste. In this study, redox mediators are used to activate the inert C−C bonds. Specifically, N‐hydroxyphthalimide (NHPI) is used as the redox mediator, which is oxidized to phthalimide‐N‐oxyl (PINO) radical to initiate hydrogen atom transfer (HAT) reactions with benzylic C−H bonds. The resulting carbon radical is readily captured by molecular oxygen to form a peroxide that decomposes into oxygenated C−C bond‐scission fragments. This indirect approach reduces the oxidation potential by >1.2 V compared to the direct oxidation of the substrate. Studies with model compounds reveal that the selectivity of C−C bond cleavage increases with decreasing C−C bond dissociation energy. With NHPI‐mediated oxidation, oligomeric styrene (OS510; Mn=510 Da) and polystyrene (PS; Mn≈10 000 Da) are converted into oxygenated monomers, dimers, and oligomers.
- Subjects
ATOM transfer reactions; ABSTRACTION reactions; HYDROGEN transfer reactions; CARBON-carbon bonds; SCISSION (Chemistry); PEROXIDES
- Publication
ChemSusChem, 2022, Vol 15, Issue 6, p1
- ISSN
1864-5631
- Publication type
Article
- DOI
10.1002/cssc.202102317