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由一种带有叔胺的多齿羧酸配体构建的两种配位聚合物,在常压下作为酸碱催化剂用于由二氧化碳合成碳酸氯丙烯酯。

Two coordination polymers constructed from a multidentate carboxylic acid ligand with a tertiary amine serve as acid-base catalysts for the synthesis of chloropropene carbonate from CO2 under atmospheric pressure.

作者信息

Chen Chao, Zhang Jun, Li Guanghua, Shen Pan, Jin Haichao, Zhang Ning

机构信息

Department of Chemistry, Nanchang University, Nanchang, 330031, P. R. China.

出版信息

Dalton Trans. 2014 Oct 7;43(37):13965-71. doi: 10.1039/c4dt00908h. Epub 2014 Aug 12.

Abstract

Two new coordination polymers, [Ni(H2O)(Hpdcd)(H2O)2]·DMF (1) and [Co(H2O)(Hpdcd)(H2O)2]·DMF (2) (H3pdcd = 1-(4-carboxyphenyl)-2,5-dimethyl, 1H-pyrrole-3,4-dicarboxylic acid), which were designed based on a tertiary amine ligand, were synthesized and characterized using multiple spectroscopy techniques, including single-crystal X-ray diffraction. These two 1D linear chains possess the properties of both a Lewis acid and organic base, which was confirmed by temperature programmed desorption of ammonia and on-line mass spectrometry (NH3-TPD-MS), and selective sorption for carbon dioxide. Due to their acid-base properties, the compounds exhibited high catalytic activity, in the absence of co-catalysts, for solvent-free synthesis of chloropropene carbonate from CO2 and epichlorohydrin under atmospheric CO2 pressure. The yields of chloropropene carbonate were 88% and 87% for 1 and 2, respectively, under the optimized conditions.

摘要

基于叔胺配体设计合成了两种新型配位聚合物,[Ni(H₂O)(Hpdcd)(H₂O)₂]·DMF (1) 和 [Co(H₂O)(Hpdcd)(H₂O)₂]·DMF (2)(H₃pdcd = 1-(4-羧基苯基)-2,5-二甲基-1H-吡咯-3,4-二羧酸),并采用包括单晶X射线衍射在内的多种光谱技术对其进行了表征。这两条一维线性链同时具有路易斯酸和有机碱的性质,这通过氨程序升温脱附和在线质谱(NH₃-TPD-MS)以及对二氧化碳的选择性吸附得到了证实。由于它们的酸碱性质,这些化合物在无共催化剂的情况下,在常压二氧化碳压力下,对由二氧化碳和环氧氯丙烷无溶剂合成碳酸氯丙烯表现出高催化活性。在优化条件下,1和2的碳酸氯丙烯产率分别为88%和87%。

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