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Synthetic Copper-(Di)oxygen Complex Generation and Reactivity Relevant to Copper Protein O2-Processing. 合成铜-(二)氧络合物的生成及与铜蛋白 O2 处理相关的反应活性。
Pub Date : 2024-01-01 Epub Date: 2024-06-20 DOI: 10.4019/bjscc.83.16
Kenneth D Karlin, Pradip Kumar Hota, Bohee Kim, Sanjib Panda, Hai Phan

Synthetic copper-dioxygen complex design, generation and characterization, play a crucial role in elucidating the structure/function of copper-based metalloenzymes, including dopamine β-monooxygenase, lytic polysaccharide monooxygenases, particulate 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 CuII-(O2 •-)(superoxide), Cu2 II-(μ-η 1:η 1-O2 2-) (trans/cis-peroxide), Cu2 II-(μ-η 2:η 2-O2 2-)(side-on peroxide) and Cun II--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 Cu2-(O2 •-)/O2 2-/-OOH moieties.

合成铜-二氧复合物的设计、生成和表征在阐明铜基金属酶的结构/功能方面发挥着至关重要的作用,这些金属酶包括多巴胺 β-单加氧酶、溶解多糖单加氧酶、微粒甲烷单加氧酶、酪氨酸酶、血色素和儿茶酚氧化酶。对于合成生物无机化学家来说,设计合适的配体来密切模拟这些酶中的可变活性位点是一项具有挑战性的任务。在这篇综述中,我们重点介绍了几个具有代表性的配体系统,它们能够稳定各种铜-二氧物种,如 CuII-(O2--)(超氧化物)、Cu2 II-(μ-η 1:η 1-O2 2-)(反式/顺式过氧化物)、Cu2 II-(μ-η 2:η 2-O2 2-)(侧过氧化物)和 Cun II--OOH(过氧化氢)物种。在此,我们将讨论这些物种所使用的配体类型、合成和光谱特征。我们还描述了反应模式,特别是通过 "NIH 转移 "机制和 Cu2-(O2 --)/O2 2-/-OOH 分子之间的热力学动力学关系发生的侧过氧化物亲电芳烃羟基化反应。
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引用次数: 0
Terminal Cobalt Imido Complexes Bearing N-Anchored Tripodal N-Heterocyclic Carbene Ligands:From Imides to Imidyls and Nitrenes 带有 N 型三足 N-杂环羰基配体的末端亚胺基钴配合物:从亚胺到亚胺基和腈
Pub Date : 2023-11-30 DOI: 10.4019/bjscc.82.2
Zihan Zhang, Karsten Meyer
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引用次数: 0
ナトリウムイオン電池とプルシアンブルー類似体 钠离子电池和普鲁士蓝类似物。
Pub Date : 2023-11-30 DOI: 10.4019/bjscc.82.29
Masashi Okubo
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引用次数: 0
The Structure and Reactivity of Metal-Oxygen/Water Complexes 金属-氧/水络合物的结构与反应活性
Pub Date : 2023-11-30 DOI: 10.4019/bjscc.82.13
S. Fukuzumi, Yong Min Lee, W. Nam
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引用次数: 0
配位高分子ガラスと融液の機能化学 配位高分子玻璃和熔体的功能化学
Pub Date : 2023-05-31 DOI: 10.4019/bjscc.81.74
Satoshi Horike
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引用次数: 0
Studies on dynamic structures constructed by anisotropic assemblies of tetracyanometallate units 四氰基钛酸盐单元各向异性组装动态结构的研究
Pub Date : 2023-05-31 DOI: 10.4019/bjscc.81.50
Ryo Ohtani
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引用次数: 0
Quantum coherent manipulation of magnetic molecules 磁性分子的量子相干操作
Pub Date : 2023-05-31 DOI: 10.4019/bjscc.81.39
Shangda Jiang, Yexin Wang, Liu Zheng, Z. Hen, Gao Song
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引用次数: 0
Studies on Biosynthesis and Catalysis of Metal-Sulfur Clusters 金属硫簇合物的生物合成与催化研究
Pub Date : 2023-05-31 DOI: 10.4019/bjscc.81.58
Kazuki Tanifuji
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引用次数: 0
金属– 酸化活性種の創出と機能解明 金属– 酸化活性种の创出と机能解明
Pub Date : 2023-05-31 DOI: 10.4019/bjscc.81.3
Shinobu Itoh
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引用次数: 0
Organometallic Superatom Complexes 有机金属超原子配合物
Pub Date : 2023-05-31 DOI: 10.4019/bjscc.81.20
Roland A. Fischer
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引用次数: 0
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Bulletin of Japan Society of Coordination Chemistry
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