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贱金属催化中的光致配体-金属电荷转移

Photoinduced Ligand-to-Metal Charge Transfer in Base-Metal Catalysis.

作者信息

Treacy S M, Rovis T

机构信息

Columbia University, Department of Chemistry, 3000 Broadway, Havemeyer Hall, New York, NY 10027, USA.

出版信息

Synthesis (Stuttg). 2024 Jul;56(13):1967-1978. doi: 10.1055/s-0042-1751518. Epub 2023 Nov 21.

Abstract

The absorption of light by photosensitizers has been shown to offer novel reactive pathways through electronic excited state intermediates, complementing ground state mechanisms. Such strategies have been applied in both photocatalysis and photoredox catalysis, driven by generating reactive intermediates from their long-lived excited states. One developing area is photoinduced ligand-to-metal charge transfer (LMCT) catalysis, in which coordination of a ligand to a metal center and subsequent excitation with light results in the formation of a reactive radical and a reduced metal center. This mini review concerns the foundations and recent developments in ligand-to-metal charge transfer in transition metal catalysis focusing on the organic transformations made possible through this mechanism.

摘要

光敏剂对光的吸收已被证明可通过电子激发态中间体提供新的反应途径,作为基态机制的补充。这些策略已应用于光催化和光氧化还原催化,通过从其长寿命激发态产生活性中间体来驱动。一个正在发展的领域是光致配体到金属的电荷转移(LMCT)催化,其中配体与金属中心配位并随后用光激发会导致形成一个活性自由基和一个还原的金属中心。本综述关注过渡金属催化中配体到金属电荷转移的基础和最新进展,重点是通过该机制实现的有机转化。

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