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Electrochemically Driven C−H Hydrogen Abstraction Processes with the Tetrachloro-Phthalimido-N-Oxyl (Cl4 PINO) Catalyst
Electroanalysis ( IF 3 ) Pub Date : 2018-04-06 , DOI: 10.1002/elan.201800147
Mark A. Buckingham 1 , William Cunningham 1 , Steven D. Bull 1 , Antoine Buchard 1 , Andrea Folli 2 , Damien M. Murphy 2 , Frank Marken 1
Affiliation  

The radical redox mediator tetrachloro-phthalimido-N-oxyl (Cl4PINO) is generated at a glassy carbon electrode and investigated for the model oxidation of primary and secondary alcohols with particular attention to reaction rates and mechanism. The two-electron oxidation reactions of a range of primary, secondary, and cyclic alcohols are dissected into an initial step based on C-H hydrogen abstraction (rate constant k1, confirmed by kinetic isotope effect) and a fast radical-radical coupling of the resulting alcohol radical with Cl4PINO to give a ketal that only slowly releases the aldehyde/ketone and redox mediator precursor back into solution (rate constant k2). In situ electrochemical EPR reveals Cl4PINO sensitivity towards moisture. DFT methods are applied to confirm and predict C-H hydrogen abstraction reactivity.

中文翻译:

使用四氯-邻苯二甲酰氨基-N-Oxyl (Cl4 PINO) 催化剂的电化学驱动的 C-H 氢提取过程

自由基氧化还原介质四氯邻苯二甲酰亚胺-N-氧基(Cl4PINO)在玻璃碳电极上产生,并研究伯醇和仲醇的模型氧化,特别注意反应速率和机理。一系列伯醇、仲醇和环醇的双电子氧化反应被分解为基于 CH 脱氢(速率常数 k1,由动力学同位素效应证实)和所得醇的快速自由基 - 自由基偶联的初始步骤与 Cl4PINO 自由基生成缩酮,该缩酮仅将醛/酮和氧化还原介体前体缓慢释放回溶液中(速率常数 k2)。原位电化学 EPR 揭示了 Cl4PINO 对水分的敏感性。DFT 方法用于确认和预测 CH 的夺氢反应。
更新日期:2018-04-06
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