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点击化学中的铜(II)-苯并三唑配位化合物:诊断反应性研究。

Copper(ii)-benzotriazole coordination compounds in click chemistry: a diagnostic reactivity study.

机构信息

Department of Chemistry, School of Life Sciences, University of Sussex, Brighton BN1 9QJ, UK.

Department of Inorganic and Analytical Chemistry, University of Debrecen, H-4032 Debrecen, Hungary.

出版信息

Dalton Trans. 2018 Aug 21;47(31):10491-10508. doi: 10.1039/c8dt01256c. Epub 2018 May 24.

DOI:10.1039/c8dt01256c
PMID:29796447
Abstract

This diagnostic study aims to shed light on the catalytic activity of a library of Cu(ii) based coordination compounds with benzotriazole-based ligands. We report herein the synthesis and characterization of five new coordination compounds formulated as [Cu(L)(MeCN)(CFSO)] (1), [Cu(L)(CFSO)] (2), [Cu(L)(MeCN)(CFSO)]·(CFSO) (3), [Cu(L)(HO)(CFSO)]·(CFSO)·2(MeCO) (4), and [Cu(L)(L)(CFSO)]·4(CFSO)·8(MeCO) (5), derived from similar nitrogen-based ligands. The homogeneous catalytic activity of these compounds along with our previously reported coordination compounds (6-13), derived from similar ligands, is tested against the well-known Cu(i)-catalysed azide-alkyne cycloaddition reaction. The optimal catalyst [Cu(L)(CFSO)] (10) activates the reaction to afford 1,4-disubstituted 1,2,3-triazoles with yields up to 98% and without requiring a reducing agent. Various control experiments are performed to optimize the method and examine parameters such as ligand variation, metal coordination geometry and environment, in order to elucidate the behaviour of the catalytic system.

摘要

这项诊断研究旨在阐明一系列基于苯并三唑的配体的 Cu(ii) 配合物库的催化活性。我们在此报告了五个新的配位化合物的合成和表征,其化学式为 [Cu(L)(MeCN)(CFSO)] (1)、[Cu(L)(CFSO)] (2)、[Cu(L)(MeCN)(CFSO)]·(CFSO) (3)、[Cu(L)(HO)(CFSO)]·(CFSO)·2(MeCO) (4) 和 [Cu(L)(L)(CFSO)]·4(CFSO)·8(MeCO) (5),它们是由类似的氮基配体制得的。这些化合物与我们之前报道的由类似配体衍生的配合物(6-13)一起进行了均相催化活性测试,用于测试著名的 Cu(i) 催化的叠氮-炔环加成反应。最优催化剂 [Cu(L)(CFSO)] (10) 激活反应,以高达 98%的产率提供 1,4-取代的 1,2,3-三唑,而无需还原剂。进行了各种控制实验以优化方法,并检查了配体变化、金属配位几何形状和环境等参数,以阐明催化体系的行为。

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