Mechanism of Phenol Oxidation by CuCl2

IF 2 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR
Shourya Gupta, Dhanusree C. Kakkarakkal, S. Chantal E. Stieber, Subrata Kundu
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引用次数: 0

Abstract

Although copper-catalyzed organic transformations are prevalent, insights into the interactions of phenols with simple copper(II) salts are not well understood. In contrast, inspired by the oxygenase-type modifications of the phenolic substrates, the reactions of substituted phenols with metastable copper–oxygen intermediates are well documented. The present report sheds light on the reactions of substituted phenols with benchtop stable CuCl2 salt and the role of a common base like triethylamine. Moreover, the reactions of substituted phenols with CuCl2 in the presence of weakly coordinating tripodal N-nitrosated ligand L3NO have been illustrated, while a closely related tripodal copper(II) complex L3HCuCl2 (2) of the corresponding non-nitrosated ligand L3H does not react with the phenolic substrates. Phenol reactions with CuCl2 in the presence of the L3NO ligand enable in depth mechanistic investigation, thereby illustrating a bimolecular rate law with ΔH = 15.13 kcal mol−1, ΔS = −9.6 eu, and kinetic isotope effect k2(ArOH)/k2(ArOD) in the range of 1.35–1.43. Thus, these findings suggest that simple copper(II) salts like CuCl2 are capable of facilitating a proton-coupled electron transfer (PCET) pathway.

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CuCl2氧化苯酚的机理
虽然铜催化的有机转化很普遍,但对苯酚与简单铜(II)盐的相互作用的了解还不是很清楚。相比之下,受酚类底物的加氧酶型修饰的启发,取代的酚类与亚稳铜氧中间体的反应得到了很好的记录。本报告阐明了取代苯酚与台面稳定CuCl2盐的反应以及三乙胺等共同碱的作用。此外,在弱配位的三脚n-亚硝化配体L3NO的存在下,取代苯酚与CuCl2的反应已经被阐明,而密切相关的三脚铜(II)配合物L3HCuCl2(2)的相应非亚硝化配体L3H不与酚底物反应。在L3NO配体存在的情况下,苯酚与CuCl2的反应进行了深入的机理研究,从而说明了一个双分子速率定律,ΔH‡= 15.13 kcal mol−1,ΔS‡=−9.6 eu,动力学同位素效应k2(ArOH)/k2(ArOD)在1.35-1.43范围内。因此,这些发现表明,像CuCl2这样简单的铜(II)盐能够促进质子耦合电子转移(PCET)途径。
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来源期刊
European Journal of Inorganic Chemistry
European Journal of Inorganic Chemistry 化学-无机化学与核化学
CiteScore
4.30
自引率
4.30%
发文量
419
审稿时长
1.3 months
期刊介绍: The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry: Chemische Berichte Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.
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