Karlin Kenneth D, Hota Pradip Kumar, Kim Bohee, Panda Sanjib, Phan Hai
Department of Chemistry, Johns Hopkins University.
Bull Jpn Soc Coord Chem. 2024;83:16-27. doi: 10.4019/bjscc.83.16. Epub 2024 Jun 20.
Synthetic copper-dioxygen complex design, generation and characterization, play a crucial role in elucidating the structure/function of copper-based metalloenzymes, including dopamine -monooxygenase, lytic polysaccharide monooxygenases, methane monooxygenase, tyrosinase, hemocyanin, and catechol oxidase. Designing suitable ligands to closely mimic the variable active sites found in these enzymes poses a challenging task for synthetic bioinorganic chemists. In this review, we have highlighted a few representative ligand systems capable of stabilizing various copper-dioxygen species such as Cu-(O )(superoxide), Cu -(- : -O ) -peroxide), Cu -(- : -O )(side-on peroxide) and Cu -OOH (hydroperoxide) species. Here, we discuss the ligand type utilized, syntheses, and spectroscopic characterization of these species. We also delineate reactivity patterns, particularly electrophilic arene hydroxylation by a side-on peroxo species which occurs via a "NIH shift" mechanism and thermodynamic-kinetic relationships among Cu-(O )/O /OOH moieties.
合成铜-双氧络合物的设计、生成及表征，在阐明包括多巴胺单加氧酶、裂解多糖单加氧酶、甲烷单加氧酶、酪氨酸酶、血蓝蛋白和儿茶酚氧化酶在内的铜基金属酶的结构/功能方面起着至关重要的作用。设计合适的配体以紧密模拟这些酶中发现的可变活性位点，对合成生物无机化学家来说是一项具有挑战性的任务。在本综述中，我们重点介绍了一些能够稳定各种铜-双氧物种的代表性配体体系，如Cu-(O )（超氧化物）、Cu -(- : -O ) -过氧化物）、Cu -(- : -O )（侧基过氧化物）和Cu -OOH（氢过氧化物）物种。在此，我们讨论了这些物种所使用的配体类型、合成方法和光谱表征。我们还描述了反应模式，特别是通过侧基过氧物种进行的亲电芳烃羟基化反应，该反应通过“NIH转移”机制发生，以及Cu-(O )/O /OOH部分之间的热力学-动力学关系。
