Department of Chemistry, Wuhan University, Wuhan, 430072, China.
Angew Chem Int Ed Engl. 2023 Mar 13;62(12):e202219302. doi: 10.1002/anie.202219302. Epub 2023 Feb 8.
The in-depth study of electrochemical (EC) synthesis can require a powerful mass spectrometry (MS) analytical platform which can discover and identify fleeting intermediates in EC reactions. Here we report a floating electrolytic electrospray ionization (FE-ESI) strategy that can perform EC processes in a floating electrolytic cell and monitor intermediates by high-resolution MS. Compared with previous EC-MS methods, a significant advantage of FE-ESI-MS is that it allows one to modulate the electrolytic and electrospray process individually, ensuring its high sensitivity in discovering intermediates and universality to investigate redox reactions in different scenarios. This powerful platform has been successfully used to investigate the EC reductive coupling of p-tolylboronic acid and p-nitrotoluene. A series of nitrene intermediates were discovered and identified by FE-ESI-MS, indicating that a hidden mechanism involving nitrene formation might play a key role in EC reductive coupling process.
深入研究电化学（EC）合成可能需要一个强大的质谱（MS）分析平台，该平台能够发现和识别 EC 反应中的短暂中间体。在这里，我们报告了一种浮动电解电喷雾电离（FE-ESI）策略，该策略可以在浮动电解池中进行 EC 过程，并通过高分辨率 MS 监测中间体。与以前的 EC-MS 方法相比，FE-ESI-MS 的一个显著优势是它允许单独调节电解和电喷雾过程，确保其在发现中间体方面具有高灵敏度，并普遍适用于研究不同情况下的氧化还原反应。这个强大的平台已成功用于研究对甲苯硼酸和对硝基甲苯的 EC 还原偶联。通过 FE-ESI-MS 发现并鉴定了一系列氮宾中间体，表明可能存在涉及氮宾形成的隐藏机制在 EC 还原偶联过程中起关键作用。
