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URJC-1:用于O-芳基化交叉偶联的稳定高效催化剂。

URJC-1: Stable and Efficient Catalyst for O-Arylation Cross-Coupling.

作者信息

García-Rojas Elena, Leo Pedro, Tapiador Jesús, Martos Carmen, Orcajo Gisela

机构信息

Chemical and Environmental Engineering Group, ESCET, Rey Juan Carlos University, C/Tulipán s/n, 28933 Móstoles, Spain.

出版信息

Nanomaterials (Basel). 2024 Jun 27;14(13):1103. doi: 10.3390/nano14131103.

Abstract

The design of metal-organic frameworks (MOFs) allows the definition of properties for their final application in small-scale heterogeneous catalysis. Incorporating various catalytic centers within a single structure can produce a synergistic effect, which is particularly intriguing for cross-coupling reactions. The URJC-1 material exhibits catalytic duality: the metal centers act as Lewis acid centers, while the nitrogen atoms of the organic ligand must behave as basic centers. The impact of reaction temperature, catalyst concentration, and basic agent concentration was evaluated. Several copper-based catalysts, including homogeneous and heterogeneous MOF catalysts with and without the presence of nitrogen atoms in the organic ligand, were assessed for their catalytic effect under optimal conditions. Among the catalysts tested, URJC-1 exhibited the highest catalytic activity, achieving complete conversion of 4-nitrobenzaldehyde with only 3% mol copper concentration in one hour. Furthermore, URJC-1 maintained its crystalline structure even after five reaction cycles, demonstrating remarkable stability in the reaction medium. The study also examined the impact of various substituents of the substrate alcohol on the reaction using URJC-1. The results showed that the reaction had high activity when activating substituents were present and for most cyclic alcohols rather than linear ones.

摘要

金属有机框架(MOF)的设计使其能够为在小规模非均相催化中的最终应用定义性质。在单一结构中引入各种催化中心可产生协同效应,这对于交叉偶联反应尤其具有吸引力。URJC-1材料具有催化双重性:金属中心充当路易斯酸中心,而有机配体的氮原子必须充当碱性中心。评估了反应温度、催化剂浓度和碱试剂浓度的影响。在最佳条件下,评估了几种铜基催化剂,包括有机配体中有无氮原子的均相和非均相MOF催化剂的催化效果。在所测试的催化剂中,URJC-1表现出最高的催化活性,在一小时内仅用3%摩尔浓度的铜就能实现4-硝基苯甲醛的完全转化。此外,即使经过五个反应循环,URJC-1仍保持其晶体结构,在反应介质中表现出显著的稳定性。该研究还使用URJC-1研究了底物醇的各种取代基对反应的影响。结果表明,当存在活化取代基时,反应具有高活性,并且对于大多数环状醇而非直链醇也是如此。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/367f/11243573/5e825b20e9b1/nanomaterials-14-01103-sch001.jpg

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