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Recent progress in oxidation chemistry of high-valent ruthenium-oxo and osmium-oxo complexes and related species
Coordination Chemistry Reviews ( IF 20.3 ) Pub Date : 2022-05-11 , DOI: 10.1016/j.ccr.2022.214536
Tomoya Ishizuka 1 , Hideki Sugimoto 2 , Shinobu Itoh 2, 3 , Takahiko Kojima 1, 3
Affiliation  

Ruthenium and osmium complexes are playing important roles in stoichiometric and catalytic oxidation reactions to achieve unique chemical conversion of inorganic and organic compounds. Bio-inspired oxidation reactions have been developed using ruthenium and osmium complexes on the basis of peroxide activation and proton-coupled electron transfer (PCET) to generate high-valent Ru-oxo (Ru=O) and Os-oxo (Os=O) complexes, which can be characterized spectroscopic and crystallographic methods, as reactive species. The fairly high stability and also reactivity of high-valent Ru=O and Os=O complexes allow us to gain detailed mechanistic insights into oxidation reactions, including hydrogen atom transfer from organic compounds to those complexes. As for high-valent Ru-oxo complexes, which can be formed through PCET oxidation of lower-valent Ru-aqua complexes, we describe their reactivity in oxidation of water and organic compounds such as alcohols and alkanes. As related species, Ru-oxyl (Ru-O•) complexes that bear radical character at the oxo ligands are also included to discuss on their unique reactivity including oxidative cracking of aromatic compounds and radical coupling. Concerning high-valent Os-oxo complexes which are formed through peroxide activation or oxygen atom transfer (OAT), unique reactivity has been demonstrated to perform cis-selective dihydroxylation of alkenes as well as C–H activation.



中文翻译:

高价钌-氧和锇-氧配合物及相关物质的氧化化学研究进展

钌和锇配合物在化学计量和催化氧化反应中发挥着重要作用,以实现无机和有机化合物的独特化学转化。在过氧化物活化和质子耦合电子转移 (PCET) 的基础上,使用钌和锇配合物开发了仿生氧化反应,以产生高价 Ru-oxo (Ru=O) 和 Os-oxo (Os=O)配合物,可以用光谱和晶体学方法表征为活性物质。高价 Ru=O 和 Os=O 配合物相当高的稳定性和反应性使我们能够获得对氧化反应的详细机理见解,包括从有机化合物到这些配合物的氢原子转移。至于高价的 Ru-oxo 配合物,可以通过 PCET 氧化较低价的 Ru-aqua 配合物形成,我们描述了它们在氧化水和有机化合物(如醇和烷烃)中的反应性。作为相关物种,还包括在氧代配体上具有自由基特征的Ru-oxyl(Ru-O•)配合物,以讨论它们独特的反应性,包括芳族化合物的氧化裂解和自由基偶联。关于通过过氧化物活化或氧原子转移 (OAT) 形成的高价 Os-oxo 配合物,已证明其独特的反应性可用于 还包括在氧代配体上具有自由基特征的Ru-氧基(Ru-O•)配合物,以讨论它们独特的反应性,包括芳香族化合物的氧化裂解和自由基偶联。关于通过过氧化物活化或氧原子转移 (OAT) 形成的高价 Os-oxo 配合物,已证明其独特的反应性可用于 还包括在氧代配体上具有自由基特征的Ru-氧基(Ru-O•)配合物,以讨论它们独特的反应性,包括芳香族化合物的氧化裂解和自由基偶联。关于通过过氧化物活化或氧原子转移 (OAT) 形成的高价 Os-oxo 配合物,已证明其独特的反应性可用于烯烃的顺式选择性二羟基化以及 C-H 活化。

更新日期:2022-05-12
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