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由三乙醇胺和均苯四甲酸衍生的铜(II)配位聚合物用于环己烷的仿生温和过氧化氧化反应。

Copper(II) coordination polymers derived from triethanolamine and pyromellitic acid for bioinspired mild peroxidative oxidation of cyclohexane.

作者信息

Karabach Yauhen Y, Kirillov Alexander M, Haukka Matti, Kopylovich Maximilian N, Pombeiro Armando J L

机构信息

Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, TU Lisbon, Avenue Rovisco Pais, 1049-001 Lisbon, Portugal.

出版信息

J Inorg Biochem. 2008 May-Jun;102(5-6):1190-4. doi: 10.1016/j.jinorgbio.2007.11.007. Epub 2007 Nov 29.

Abstract

The new inorganic 1D coordination polymer [Cu2(H3tea)2(mu4-pma)]n has been prepared, via self-assembly in aqueous medium, from copper(II) nitrate, triethanolamine (H3tea), pyromellitic acid (H4pma) and lithium hydroxide, and characterized by IR spectroscopy, elemental and single-crystal X-ray diffraction analyses. This compound and the related 2D polymer [Cu2(mu-H2tea)(2){mu3-Na2(H2O)4}(mu6-pma)]n.10nH2O are shown to mimic the alkane partial oxidation activity of the multicopper particulate methane monooxygenase, acting as catalysts precursors for the peroxidative oxidation of cyclohexane into cyclohexanol and cyclohexanone, by hydrogen peroxide (as green oxidant) and at room temperature in acidic MeCN/H2O medium. An overall yield (based on cyclohexane) of 29% has been achieved.

摘要

新型无机一维配位聚合物[Cu2(H3tea)2(μ4 - pma)]n已通过在水介质中自组装,由硝酸铜(II)、三乙醇胺(H3tea)、均苯四甲酸(H4pma)和氢氧化锂制备而成,并通过红外光谱、元素分析和单晶X射线衍射分析进行了表征。该化合物以及相关的二维聚合物[Cu2(μ - H2tea)(2){μ3 - Na2(H2O)4}(μ6 - pma)]n·10nH2O被证明可模拟多铜颗粒甲烷单加氧酶的烷烃部分氧化活性,在酸性MeCN/H2O介质中,于室温下作为过氧化氢(作为绿色氧化剂)将环己烷过氧化氧化为环己醇和环己酮的催化剂前体。已实现基于环己烷的总产率为29%。

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