铜（I）过氧物种介导的分子间 C-H 活化化学。
Cupric superoxo-mediated intermolecular C-H activation chemistry.
机构信息
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States.
出版信息
J Am Chem Soc. 2011 Feb 16;133(6):1702-5. doi: 10.1021/ja110466q. Epub 2011 Jan 25.
Abstract
The new cupric superoxo complex LCu(II)(O(2)(•-)), which possesses particularly strong O-O and Cu-O bonding, is capable of intermolecular C-H activation of the NADH analogue 1-benzyl-1,4-dihydronicotinamide (BNAH). Kinetic studies indicated a first-order dependence on both the Cu complex and BNAH with a deuterium kinetic isotope effect (KIE) of 12.1, similar to that observed for certain copper monooxygenases.
摘要
新型的铜过氧配合物LCu(II)(O(2)(•-))具有特别强的 O-O 和 Cu-O 键，能够实现 NADH 类似物 1-苄基-1,4-二氢烟酰胺（BNAH）的分子间 C-H 活化。动力学研究表明，该反应对铜配合物和 BNAH 均呈一级依赖，氘代动力学同位素效应（KIE）为 12.1，与某些铜单加氧酶的观察结果相似。
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本文引用的文献
1
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2
Generating Cu(II)-oxyl/Cu(III)-oxo species from Cu(I)-alpha-ketocarboxylate complexes and O2: in silico studies on ligand effects and C-H-activation reactivity.
Chemistry. 2009;15(19):4886-95. doi: 10.1002/chem.200802338.
3
High-valent manganese(v)-oxo porphyrin complexes in hydride transfer reactions.
Chem Commun (Camb). 2009 Feb 14(6):704-6. doi: 10.1039/b814928c. Epub 2008 Dec 19.
4
Copper-dioxygen complex mediated C-H bond oxygenation: relevance for particulate methane monooxygenase (pMMO).
Curr Opin Chem Biol. 2009 Feb;13(1):119-31. doi: 10.1016/j.cbpa.2009.02.025. Epub 2009 Mar 13.
5
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6
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