Kojima Takahiko
Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.
Dalton Trans. 2020 Jun 9;49(22):7284-7293. doi: 10.1039/d0dt00898b.
Proton-coupled electron transfer (PCET) is one of the ubiquitous and fundamental processes in various redox reactions performed by transition-metal complexes. In this article, we describe our remarkable achievements related to PCET in metal complexes, including proton manipulation of ligands to afford molecular bistability involving reversible intramolecular PCET and emergence of novel electronic structures, formation and reactivity of RuIV-oxo and RuIII-oxyl complexes, and mechanistic insights into PCET reactions from O-H and C-H bonds to RuIII-pterin complexes.
质子耦合电子转移(PCET)是过渡金属配合物进行的各种氧化还原反应中普遍存在的基本过程之一。在本文中,我们描述了我们在金属配合物中与PCET相关的显著成就,包括对配体进行质子操控以实现涉及可逆分子内PCET的分子双稳态和新型电子结构的出现、RuIV-氧代和RuIII-氧基配合物的形成及反应性,以及对从O-H和C-H键到RuIII-蝶呤配合物的PCET反应的机理见解。