Sandford Christopher, Edwards Martin A, Klunder Kevin J, Hickey David P, Li Min, Barman Koushik, Sigman Matthew S, White Henry S, Minteer Shelley D
Department of Chemistry , University of Utah , 315 South 1400 East , Salt Lake City , Utah 84112 , USA . Email:
Chem Sci. 2019 May 23;10(26):6404-6422. doi: 10.1039/c9sc01545k. eCollection 2019 Jul 14.
Monitoring reactive intermediates can provide vital information in the study of synthetic reaction mechanisms, enabling the design of new catalysts and methods. Many synthetic transformations are centred on the alteration of oxidation states, but these redox processes frequently pass through intermediates with short life-times, making their study challenging. A variety of electroanalytical tools can be utilised to investigate these redox-active intermediates: from voltammetry to spectroelectrochemistry and scanning electrochemical microscopy. This perspective provides an overview of these tools, with examples of both electrochemically-initiated processes and monitoring redox-active intermediates formed chemically in solution. The article is designed to introduce synthetic organic and organometallic chemists to electroanalytical techniques and their use in probing key mechanistic questions.
监测反应中间体可为合成反应机理的研究提供重要信息,有助于新型催化剂和方法的设计。许多合成转化都围绕氧化态的改变展开,但这些氧化还原过程常常会经过寿命较短的中间体,这使得对它们的研究颇具挑战性。可以利用多种电分析工具来研究这些氧化还原活性中间体:从伏安法到光谱电化学和扫描电化学显微镜。本综述概述了这些工具,并列举了电化学引发过程以及监测溶液中化学形成的氧化还原活性中间体的实例。本文旨在向合成有机化学家和有机金属化学家介绍电分析技术及其在探究关键机理问题中的应用。