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铁光氧化还原催化:过去、现在和未来。

Iron Photoredox Catalysis-Past, Present, and Future.

机构信息

Centre for Analysis and Synthesis, Lund University, Lund SE-22100, Sweden.

出版信息

J Am Chem Soc. 2023 May 3;145(17):9369-9388. doi: 10.1021/jacs.3c01000. Epub 2023 Apr 20.

Abstract

Photoredox catalysis of organic reactions driven by iron has attracted substantial attention throughout recent years, due to potential environmental and economic benefits. In this Perspective, three major strategies were identified that have been employed to date to achieve reactivities comparable to the successful noble metal photoredox catalysis: (1) Direct replacement of a noble metal center by iron in archetypal polypyridyl complexes, resulting in a metal-centered photofunctional state. (2) In situ generation of photoactive complexes by substrate coordination where the reactions are driven via intramolecular electron transfer involving charge-transfer states, for example, through visible-light-induced homolysis. (3) Improving the excited-state lifetimes and redox potentials of the charge-transfer states of iron complexes through new ligand design. We seek to give an overview and evaluation of recent developments in this rapidly growing field and, at the same time, provide an outlook on the future of iron-based photoredox catalysis.

摘要

近年来,由于潜在的环境和经济效益,铁驱动的光氧化还原催化有机反应引起了广泛关注。在这篇观点文章中,确定了迄今为止采用的三种主要策略,以实现与成功的贵金属光氧化还原催化相当的反应活性:(1) 通过在典型的多吡啶配合物中直接取代贵金属中心来实现,从而产生金属中心的光功能态。(2) 通过底物配位原位生成光活性配合物,其中反应通过涉及电荷转移态的分子内电子转移来驱动,例如通过可见光诱导的均裂。(3) 通过新的配体设计来提高铁配合物的电荷转移态的激发态寿命和氧化还原电位。我们旨在对这一快速发展领域的最新进展进行概述和评估,同时展望基于铁的光氧化还原催化的未来。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2031/10161236/d9ddd8fd129b/ja3c01000_0001.jpg

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