Advances in (spectroscopic) characterization of the unusual electronic structures of open-shell cobalt complexes bearing redox-active ligands, combined with detailed mapping of their reactivity, have uncovered several new catalytic radical-type protocols that make efficient use of the synergistic properties of redox-active ligands, redox-active substrates, and the metal to which they coordinate. In this perspective, we discuss the tools available to study, induce, and control catalytic radical-type reactions with redox-active ligands and/or substrates, contemplating recent developments in the field, including some noteworthy tools, methods, and reactions developed in our own group. The main topics covered are (i) tools to characterize redox-active ligands; (ii) novel synthetic applications of catalytic reactions that make use of redox-active carbene and nitrene substrates at open-shell cobalt–porphyrins; (iii) development of catalytic reactions that take advantage of purely ligand- and substrate-based redox processes, coupled to cobalt-centered spin-changing events in a synergistic manner; and (iv) utilization of redox-active ligands to influence the spin state of the metal. Redox-active ligands have emerged as useful tools to generate and control reactive metal-coordinated radicals, which give access to new synthetic methodologies and intricate (electronic) structures, some of which are yet to be exposed.

中文翻译：

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用氧化还原活性配体和底物控制催化中的自由基型单电子基本步骤

带有氧化还原活性配体的开壳钴配合物的不寻常电子结构的（光谱）表征的进展，结合其反应性的详细映射，揭示了几种新的催化自由基类型的协议，这些协议有效地利用了氧化还原的协同特性-活性配体、氧化还原活性底物和它们配位的金属。从这个角度来看，我们讨论了可用于研究、诱导和控制具有氧化还原活性配体和/或底物的催化自由基型反应的工具，并考虑该领域的最新发展，包括在我们的研究中开发的一些值得注意的工具、方法和反应。自己的组。涵盖的主要主题是 ( i ) 表征氧化还原活性配体的工具；(二) 在开壳钴卟啉上利用氧化还原活性卡宾和氮烯底物的催化反应的新合成应用；( iii ) 开发利用纯配体和底物氧化还原过程的催化反应，以协同方式与以钴为中心的自旋变化事件相结合；( iv ) 利用氧化还原活性配体来影响金属的自旋状态。氧化还原活性配体已成为生成和控制反应性金属配位自由基的有用工具，这提供了新的合成方法和复杂的（电子）结构，其中一些尚未暴露。