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近年来，可见光介导的第一过渡周期金属催化在有机合成中展现出巨大的潜力。与传统的贵金属光催化剂（如铱和钌）相比，第一过渡周期金属（如铁、铜和钴）以其廉价和丰富的特点，正在推动绿色化学的研究。尽管第一过渡周期金属配合物的光激发态寿命比铑和铱光催化剂要短，但可以通过合理设计配体有效地提高其光催化活性。可见光介导的第一过渡周期金属催化主要有两种反应路径：（1）激发态的第一过渡周期金属配合物发生配体-金属电荷转移（LMCT）过程产生自由基活性物种参与反应；（2）激发态的第一过渡周期金属配合物与底物分子之间发生单电子转移（SET）过程产生活性物种参与反应。本文主要概述以第二种反应路径催化有机转化的近五年的研究进展。
Abstract：In recent years, first-row transition metal(FRTM) photocatalysis has shown great potential in organic synthesis. Compared with traditional noble metal photocatalysts(such as iridium and ruthenium), firstrow transition metals(such as iron, copper and cobalt) are driving the research of green chemistry due to their lower costs and higher abundance. Although the photoexcited state lifetime of the first-row transition metal complexes is shorter than that of the photocatalysts of rhodium and iridium, their photocatalytic activity can be effectively improved by rationally designing ligands. There are two main reaction pathways for visible-light mediated first-row transition metal catalysis:( 1) the excited state of first-row transition metal complexes undergoes ligand-metal charge transfer(LMCT) producing free radical active species to participate in the reaction;(2) the excited state of first-row transition metal complexes undergoes single electron transfer(SET) between substrate molecules producing active species to participate in the reaction. This article summarizes the research progress of catalyzing organic transformations via the second reaction pathway in the past five years.
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基本信息:
中图分类号:O644.1;O643.36
引用信息:
[1]郭福虎,孙志凡,丁蓓,等.第一过渡周期金属参与的光催化反应研究进展[J].新兴科学和技术趋势,2025,4(02):129-145.
基金信息:
北京分子科学国家研究中心项目(BNLMS202411); 国家自然科学基金(22373067;22222701); 科技部重点研发计划(2024YFA0917503); 勃林格殷格翰青年研究员基金(2025-03-01)
2025-03-12
2025
2025-04-24
2025
1
2025-05-21
2025-05-21
2025-05-21