Ru(III)-OCl 中间态的光谱特征：卤过氧化物酶的结构模拟物。
Spectroscopic characterization of a Ru(III)-OCl intermediate: a structural mimic of haloperoxidase enzymes.
机构信息
Southern Laboratories-208A, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India.
出版信息
Dalton Trans. 2022 Aug 30;51(34):12848-12854. doi: 10.1039/d2dt01947g.
Haloperoxidase enzymes utilize metal hypohalite species to halogenate aliphatic and aromatic C-H bonds to C-X (X = Cl, Br, I) in nature. In this work, we report the synthesis and spectroscopic characterization of a unique Ru-OCl species as a structural mimic of haloperoxidase enzymes. The reaction of [(BnTPEN)Ru(NCCH)] (BnTPEN = -benzyl-,,-tris(pyridine-2-ylmethyl)ethane-1,2-diamine) with hypochlorite in the presence of an acid in CHCN : HO mixtures generated a novel [(BnTPEN)Ru-OCl] species that persists for 4.5 h at room temperature. This new species was characterized by UV-vis absorption, EPR, and resonance Raman spectroscopic techniques, and ESI-MS. The Ru-OCl species is capable of performing oxygen atom transfer and hydrogen atom abstraction to various organic substrates.
过氧化物酶利用金属次卤酸盐物种将脂肪族和芳香族 C-H 键卤化生成 C-X（X=Cl、Br、I）。在这项工作中，我们报告了一种独特的 Ru-OCl 物种的合成和光谱表征，该物种作为过氧化物酶的结构模拟物。在 CHCN 和 HO 的混合物中，[(BnTPEN)Ru(NCCH)]（BnTPEN= -苄基-，-三（吡啶-2-基甲基）乙烷-1,2-二胺）与次氯酸盐在酸存在下反应，生成了一种在室温下持续 4.5 小时的新型[(BnTPEN)Ru-OCl]物种。该新物种通过紫外可见吸收、电子顺磁共振和共振拉曼光谱技术以及 ESI-MS 进行了表征。Ru-OCl 物种能够对各种有机底物进行氧原子转移和氢原子提取。
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