Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, University of Liège, Allée du 6 Août, Building B6A, Agora Square, 4000 Liège, Belgium.
Chem Rev. 2019 Jun 26;119(12):6906-6955. doi: 10.1021/acs.chemrev.8b00715. Epub 2019 Apr 9.
Organocobalt(III) complexes (R-Co), defined as cobalt complexes featuring a carbon-cobalt bond, are largely used to produce carbon-centered radicals by homolytic cleavage of their C-Co bond under mild conditions. They are key compounds in cutting-edge developments in the fields of organic chemistry, biochemistry, medical research, radical reactions, and organometallic chemistry. This is the first Review of the use of R-Co in both organic and polymer chemistries. Although pioneering works in organic synthesis have largely contributed to the implementation of R-Co in polymer design, the two fields have evolved independently, with many breakthroughs on both sides. The main motivation of this Review is to confront both fields to stimulate cross-fertilization. It notably describes the most important synthetic pathways for R-Co, the influence of the ligand structure and the environment of the complex on the C-Co bond strength, the modes of formation of the radicals, and the most relevant R-Co-promoted radical reactions, with a focus on the main reaction mechanisms.
有机钴(III)配合物（R-Co），定义为具有碳-钴键的钴配合物，通过其 C-Co 键的均裂在温和条件下大量用于产生碳中心自由基。它们是有机化学、生物化学、医学研究、自由基反应和金属有机化学等前沿领域发展的关键化合物。这是第一篇关于 R-Co 在有机和聚合物化学中的应用的综述。尽管有机合成中的开创性工作在很大程度上促进了 R-Co 在聚合物设计中的应用，但这两个领域是独立发展的，双方都有许多突破。本综述的主要动机是将这两个领域进行对比，以促进它们之间的交叉融合。它特别描述了 R-Co 的最重要的合成途径、配体结构和环境对 C-Co 键强度的影响、自由基的形成方式以及最重要的 R-Co 促进的自由基反应，重点介绍了主要的反应机制。
