Juliá Fabio
Facultad de Química, Centro de Investigación Multidisciplinar Pleiades-Vitalis, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain.
ACS Catal. 2025 Mar 5;15(6):4665-4680. doi: 10.1021/acscatal.4c07962. eCollection 2025 Mar 21.
Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected for many decades by careful selection of metal centers and ligands, giving rise to synthetic methods with unparalleled efficiency and chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful tool to dramatically alter the outcome of catalytic reactions, providing access to innovative pathways with remarkable synthetic potential. In this context, the adoption of photochemical conditions as a mainstream strategy to drive organic reactions has unveiled exciting opportunities to exploit the rich excited-state framework of transition metals for catalytic applications. This Perspective examines advances in the application of transition metal complexes as standalone photocatalysts, exploiting the innate reactivity of their excited states beyond their common use as photoredox catalysts. An account of relevant examples is dissected to provide a discussion on the electronic reorganization, the orbitals involved, and the associated reactivity of different types of excited states. This analysis aims to provide practitioners with fundamental principles and guiding strategies to understand, design, and apply light-activation strategies to homogeneous transition metal catalysis for organic synthesis.
过渡金属催化是有机合成中不可或缺的工具，几十年来，通过精心选择金属中心和配体，这一工具得到了利用、调控和完善，产生了具有无与伦比的效率和化学选择性的合成方法。最近的进展表明，光照射也可以作为一种强大的工具，极大地改变催化反应的结果，为具有显著合成潜力的创新途径提供了可能。在此背景下，采用光化学条件作为驱动有机反应的主流策略，为利用过渡金属丰富的激发态框架进行催化应用带来了令人兴奋的机遇。本综述探讨了过渡金属配合物作为独立光催化剂的应用进展，利用其激发态的固有反应性，而不仅仅是将其用作光氧化还原催化剂。剖析了相关实例，以讨论电子重组、涉及的轨道以及不同类型激发态的相关反应性。该分析旨在为从业者提供基本原则和指导策略，以理解、设计光活化策略并将其应用于均相过渡金属催化的有机合成。
