在酸存在下用锰(IV)双(羟)配合物氧化萘。
Oxidation of Naphthalene with a Manganese(IV) Bis(hydroxo) Complex in the Presence of Acid.
机构信息
Department of Emerging Materials Science, DGIST, Daegu, 42988, Korea.
Department of Chemistry, Stanford University, Stanford, CA, 94305, USA.
出版信息
Angew Chem Int Ed Engl. 2018 Jun 25;57(26):7764-7768. doi: 10.1002/anie.201802641. Epub 2018 May 22.
Abstract
Naphthalene oxidation with metal-oxygen intermediates is a difficult reaction in environmental and biological chemistry. Herein, we report that a Mn bis(hydroxo) complex, which was fully characterized by various physicochemical methods, such as ESI-MS, UV/Vis, and EPR analysis, X-ray diffraction, and XAS, can be employed for the oxidation of naphthalene in the presence of acid to afford 1,4-naphthoquinone. Redox titration of the Mn bis(hydroxo) complex gave a one-electron reduction potential of 1.09 V, which is the most positive potential for all reported nonheme Mn bis(hydroxo) species as well as Mn oxo analogues. Kinetic studies, including kinetic isotope effect analysis, suggest that the naphthalene oxidation occurs through a rate-determining electron transfer process.
摘要
萘的金属-氧中间体氧化是环境和生物化学中的一个难题。在此，我们报道了一种 Mn 双(羟)配合物，它通过各种物理化学方法（如 ESI-MS、UV/Vis 和 EPR 分析、X 射线衍射和 XAS）得到了充分的表征，在酸存在下可以用于萘的氧化，得到 1,4-萘醌。Mn 双(羟)配合物的氧化还原滴定给出了 1.09 V 的单电子还原电位，这是所有报道的非血红素 Mn 双(羟)物种以及 Mn 氧类似物中最正的电位。动力学研究，包括动力学同位素效应分析，表明萘的氧化是通过一个决定速率的电子转移过程发生的。
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