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Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators.

ABSTRACT: The generation and intermolecular functionalisation of carbon-centred radicals has broad potential synthetic utility. Herein, we show that benzylic radicals may be generated electrochemically from benzylboronate derivatives at low electrode potentials (ca. -0.3 V vs. Cp2Fe0/+) via single electron oxidation. Use of a catalytic quantity of a ferrocene-based electron-transfer mediator is crucial to achieve successful radical functionalisation and avoid undesirable side reactions arising from direct electrochemical oxidation or from the use of stoichiometric ferrocenium-based oxidants.

SUBMITTER: Lennox AJJ

PROVIDER: S-EPMC5909123 | biostudies-literature | 2018 Jan

REPOSITORIES: biostudies-literature

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Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators.

Lennox Alastair J J AJJ Nutting Jordan E JE Stahl Shannon S SS

Chemical science 20171106 2

The generation and intermolecular functionalisation of carbon-centred radicals has broad potential synthetic utility. Herein, we show that benzylic radicals may be generated electrochemically from benzylboronate derivatives at low electrode potentials (ca. -0.3 V vs. Cp2Fe0/+) via single electron oxidation. Use of a catalytic quantity of a ferrocene-based electron-transfer mediator is crucial to achieve successful radical functionalisation and avoid und ...[more]

PMID: 29732109

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Project description:BackgroundExtracellular electron transfer (EET) is essential in improving the power generation performance of electrochemically active bacteria (EAB) in microbial fuel cells (MFCs). Currently, the EET mechanisms of dissimilatory metal-reducing (DMR) model bacteria Shewanella oneidensis and Geobacter sulfurreducens have been thoroughly studied. Klebsiella has also been proved to be an EAB capable of EET, but the EET mechanism has not been perfected. This study investigated the effects of biofilm transfer and electron mediators transfer on Klebsiella quasipneumoniae sp. 203 electricity generation performance in MFCs.ResultsHerein, we covered the anode of MFC with a layer of microfiltration membrane to block the effect of the biofilm mechanism, and then explore the EET of the electron mediator mechanism of K. quasipneumoniae sp. 203 and electricity generation performance. In the absence of short-range electron transfer, we found that K. quasipneumoniae sp. 203 can still produce a certain power generation performance, and coated-MFC reached 40.26 mW/m2 at a current density of 770.9 mA/m2, whereas the uncoated-MFC reached 90.69 mW/m2 at a current density of 1224.49 mA/m2. The difference in the electricity generation performance between coated-MFC and uncoated-MFC was probably due to the microfiltration membrane covered in anode, which inhibited the growth of EAB on the anode. Therefore, we speculated that K. quasipneumoniae sp. 203 can also perform EET through the biofilm mechanism. The protein content, the integrity of biofilm and the biofilm activity all proved that the difference in the electricity generation performance between coated-MFC and uncoated-MFC was due to the extremely little biomass of the anode biofilm. To further verify the effect of electron mediators on electricity generation performance of MFCs, 10 µM 2,6-DTBBQ, 2,6-DTBHQ and DHNA were added to coated-MFC and uncoated-MFC. Combining the time-voltage curve and CV curve, we found that 2,6-DTBBQ and 2,6-DTBHQ had high electrocatalytic activity toward the redox reaction of K. quasipneumoniae sp. 203-inoculated MFCs. It was also speculated that K. quasipneumoniae sp. 203 produced 2,6-DTBHQ and 2,6-DTBBQ.ConclusionsTo the best of our knowledge, the three modes of EET did not exist separately. K. quasipneumoniae sp.203 will adopt the corresponding electron transfer mode or multiple ways to realize EET according to the living environment to improve electricity generation performance.

Dataset Information

Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators.

Publications

Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators.

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