Trinuclear Co(II)-Based Metal–Organic Framework as a Heterogeneous Catalyst for the Ring-Opening Reaction of Epoxides

IF 4.7 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Mengzhen Xu, Zhenyu Geng, Shuhan Zhang, Lu Yang*, Rui Zhao, Hui Wang, Zhihao Yu, Daopeng Zhang*, Haining Wang, Suna Wang and Zhen Zhou*, 
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Abstract

The ring-opening of epoxides plays a crucial role in synthesizing antitumoral pharmaceuticals and fine chemicals, and the key lies in the rational design of highly efficient catalysts. Herein, by using 4-(2-carboxyethenyl)benzoic acid and 1,10-phenanthroline (phen) hydrate as mixed ligands, a new Co(II)-based porous metal–organic framework (Co-CBA) has been synthesized via a solvothermal reaction. Structural analysis revealed that Co-CBA features unique trinuclear clusters as building blocks, which link with the ligands to form a sequentially porous two-dimensional network. The appropriate pore channels and high density of metal active clusters in Co-CBA facilitate its exceptional catalytic performance as a heterogeneous catalyst in the ring-opening reaction of epoxy chloropropane with methanol. Under optimal conditions, this catalyst achieves >99% conversion and >99% selectivity for the target product 1-chloro-3-methoxypropan-2-ol within 28 h. In addition, Co-CBA also displays excellent substrate compatibility, outstanding reusability, and robust structural stability after the catalysis. A plausible reaction pathway for the ring-opening of epoxides has also been proposed.

Abstract Image

三核Co(II)基金属-有机骨架作为环氧化合物开环反应的非均相催化剂
环氧化合物开环在抗肿瘤药物和精细化学品的合成中起着至关重要的作用,其关键在于合理设计高效的催化剂。本文以4-(2-羧基乙基)苯甲酸和1,10-菲罗啉(phen)水合物为混合配体,通过溶剂热反应合成了一种新型的Co(II)基多孔金属有机骨架(Co- cba)。结构分析表明,Co-CBA具有独特的三核簇作为构建单元,与配体连接形成有序的多孔二维网络。在环氧氯丙烷与甲醇的开环反应中,Co-CBA具有合适的孔道和高密度的金属活性团簇,使其具有优异的非均相催化性能。在最优条件下,该催化剂在28 h内对目标产物1-氯-3-甲氧基丙烷-2-醇的转化率达到99%,选择性达到99%。此外,催化后Co-CBA还表现出良好的底物相容性、突出的可重复使用性和较强的结构稳定性。还提出了环氧化物开环的一种合理的反应途径。
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来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
期刊介绍: Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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