Elucidation of Underlying Reactivities of Alternating Current Electrosynthesis by Time-resolved Mapping of Short-lived Reactive Intermediates.
Elucidation of Underlying Reactivities of Alternating Current Electrosynthesis by Time-resolved Mapping of Short-lived Reactive Intermediates.
复制标题
通过短寿命反应中间体的时间分辨映射阐明交流电合成的潜在反应性。
DOI：
10.1002/anie.202306460
复制
发表时间：
2023
影响因子：
--
通讯作者：
Suming Chen
中科院分区：
文献类型：
--
作者：
Qiongqiong Wan;Kaixiang Chen;Xin Dong;Xianqin Ruan;Hong Yi;Suming Chen
交流电解是合成化学中的一个新兴领域，而其机理研究受到难以描述的中间过程的有效表征的挑战。在此，我们开发了一个操作电化学质谱平台，允许在直流和交流模式下逐步电合成反应中间体的时间分辨映射。通过剖析芳胺电化学功能化的关键中间过程，证明和验证了AC电合成的独特反应性，包括通过逆过程最小化过度氧化/还原，以及使成对电解中由氧化和还原产生的短寿命中间体有效反应。值得注意的是，在多步连续AC电合成中，发现了反应性N-中心自由基中间体的受控动力学，以使竞争反应最小化。总之，本研究为交流电解机理提供了直接证据，阐明了交流电解高效的根本原因，有利于交流电合成反应的合理设计。
Alternating current (AC) electrolysis is an emerging field in synthetic chemistry, while its mechanistic studies are challenged by the effective characterization of the elusive intermediate processes. Herein, we develop an operando electrochemical mass spectrometry platform that allows time-resolved mapping of stepwise electrosynthetic reactive intermediates in both direct current and alternating current modes. By dissecting the key intermediate processes of electrochemical functionalization of arylamines, the unique reactivities of AC electrosynthesis, including minimizing the over-oxidation/reduction through the inverse process, and enabling effective reaction of short-lived intermediates generated by oxidation and reduction in paired electrolysis, were evidenced and verified. Notably, the controlled kinetics of reactive N-centered radical intermediates in multi-step sequential AC electrosynthesis to minimize the competing reactions was discovered. Overall, this work provides direct evidence for the mechanism of AC electrolysis, and clarifies the underlying reasons for its high efficiency, which will benefit the rational design of AC electrosynthetic reactions.