Electrochemical Activation of C–C Bonds via Mediated Hydrogen Atom Transfer Reactions

Yan, Bing; Shi, Changxia; Beckham, Gregg T.; Chen, Eugene Y.-X.; Roman-Leshkov, Yuriy

doi:10.1002/cssc.202102317

Title: Electrochemical Activation of C–C Bonds via Mediated Hydrogen Atom Transfer Reactions

Journal Article · 19 December 2021 · ChemSusChem

DOI: https://doi.org/10.1002/cssc.202102317 · OSTI ID:1839920

Yan, Bing ^[1]; Shi, Changxia ^[2];

^[3]; Chen, Eugene Y.-X. ^[2]; Roman-Leshkov, Yuriy ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Colorado State Univ., Fort Collins, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

Activating inert sp 3 -sp 3 carbon-carbon (C-C) bonds remains a major bottleneck in the chemical upcycling of recalcitrant polyolefin waste. Here, we use redox mediators to activate the inert C-C bonds. Specifically, we use N -hydroxyphthalimide (NHPI) as the redox mediator that 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 revealed the selectivity of C-C bond cleavage increases with decreasing C-C bond dissociation energy. With NHPI-mediated oxidation, oligomeric styrene ( M n = 510 Da, OS 510 ) and polystyrene (PS, ~10,000 Da) were converted into oxygenated monomers, dimers, and oligomers.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Advanced Manufacturing Office (EE-5A); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B); BioOptimized Technologies to keep Thermoplastics out of Landfills and the Environment (BOTTLE) Consortium

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1839920

Report Number(s):: NREL/JA-2A00-81783; MainId:82556; UUID:73409701-9bd6-4057-903e-123288b98b2e; MainAdminID:63586

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Journal Issue: 6 Vol. 15; ISSN 1864-5631

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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09 BIOMASS FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
C-C bond activation
electrocatalysis
plastic upcycling
redox mediators

Title: Electrochemical Activation of C–C Bonds via Mediated Hydrogen Atom Transfer Reactions

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