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一种具有显著氢气和一氧化碳储存能力以及用于C(sp)-H键有氧氧化胺化反应和Biginelli反应的多相催化作用的铜(II)金属有机框架。

A Cu(ii) metal-organic framework with significant H and CO storage capacity and heterogeneous catalysis for the aerobic oxidative amination of C(sp)-H bonds and Biginelli reactions.

作者信息

Gupta Anoop K, De Dinesh, Tomar Kapil, Bharadwaj Parimal K

机构信息

Department of Chemistry, Indian Institute of Technology Kanpur, UP-208016, India.

出版信息

Dalton Trans. 2018 Jan 30;47(5):1624-1634. doi: 10.1039/c7dt04006g.

Abstract

A Cu(ii) metal-organic framework, {[Cu(L)(HO)]·(5DMF)(4HO)} (1), has been synthesized using an angular tetracarboxylic acid ligand (H4L) incorporating both trifluoromethyl (-CF) and amine (-NH) groups. Notably, the framework possesses high water and thermal stability. At atmospheric pressure, the activated framework 1' exhibits substantially high amounts of CO (35.5 and 20.8 wt% at 273 and 298 K respectively) and H (1.72 wt% at 77 K) adsorption. Also, 1' exhibits excellent catalytic activity for the condensation-cyclization reaction between 2-benzoyl pyridine and different benzylamines via oxidative amination of the C(sp)-H bond to form 1,3-diarylated imidazo[1,5-a]pyridines under mild aerobic conditions. In addition to this, 1' shows excellent heterogeneous catalytic activity in Biginelli reactions. The solid catalyst could be recycled several times without significant loss in the catalytic activities.

摘要

一种铜(II)金属有机框架化合物{[Cu(L)(HO)]·(5DMF)(4HO)} (1),已通过使用一种同时含有三氟甲基(-CF)和胺基(-NH)的角形四羧酸配体(H4L)合成。值得注意的是,该框架具有高水稳定性和热稳定性。在大气压下,活化后的框架1'对CO(在273 K和298 K时分别为35.5 wt%和20.8 wt%)和H(在77 K时为1.72 wt%)表现出大量吸附。此外,1'在温和的有氧条件下,通过C(sp)-H键的氧化胺化作用,对2-苯甲酰基吡啶与不同苄胺之间的缩合环化反应形成1,3-二芳基咪唑并[1,5-a]吡啶表现出优异的催化活性。除此之外,1'在Biginelli反应中也表现出优异的多相催化活性。该固体催化剂可以循环使用多次,而催化活性没有明显损失。

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