A molecular mediator for reductive concerted proton-electron transfers via electrocatalysis

doi:10.1126/science.abc1607

GSTDTAP > 气候变化

DOI	10.1126/science.abc1607
	A molecular mediator for reductive concerted proton-electron transfers via electrocatalysis
	Matthew J. Chalkley; Pablo Garrido-Barros; Jonas C. Peters
	2020-08-14
发表期刊	Science
出版年	2020
英文摘要	Many chemical reactions involve concurrent transfer of a proton and an electron. In electrochemical synthesis, this mechanism could prove useful in lowering the energy necessary for cathodic electron transfer alone, but it is hindered by competing direct coupling of the protons and electrons to make hydrogen instead. Chalkley et al. now report a molecular mediator consisting of a dimethylaniline base tethered to a cobaltocenium electron acceptor. This construct can deliver both a proton and an electron to a substrate from an acid and a cathode while skirting the hydrogen pathway. Science , this issue p. [850][1] Electrocatalytic approaches to the activation of unsaturated substrates via reductive concerted proton-electron transfer (CPET) must overcome competing, often kinetically dominant hydrogen evolution. We introduce the design of a molecular mediator for electrochemically triggered reductive CPET through the synthetic integration of a Brønsted acid and a redox mediator. Cathodic reduction at the cobaltocenium redox mediator substantially weakens the homolytic nitrogen-hydrogen bond strength of a Brønsted acidic anilinium tethered to one of the cyclopentadienyl rings. The electrochemically generated molecular mediator is demonstrated to transform a model substrate, acetophenone, to its corresponding neutral α-radical via a rate-determining CPET. [1]: /lookup/doi/10.1126/science.abc1607
领域	气候变化 ; 资源环境
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引用统计
文献类型	期刊论文
条目标识符	http://119.78.100.173/C666/handle/2XK7JSWQ/288094
专题	气候变化资源环境科学
推荐引用方式 GB/T 7714	Matthew J. Chalkley,Pablo Garrido-Barros,Jonas C. Peters. A molecular mediator for reductive concerted proton-electron transfers via electrocatalysis[J]. Science,2020.
APA	Matthew J. Chalkley,Pablo Garrido-Barros,&Jonas C. Peters.(2020).A molecular mediator for reductive concerted proton-electron transfers via electrocatalysis.Science.
MLA	Matthew J. Chalkley,et al."A molecular mediator for reductive concerted proton-electron transfers via electrocatalysis".Science (2020).