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三种用铜(II)胺配合物改性的有机-无机聚氧铌酸盐基化合物:苯乙烯氧化反应的合成、表征及催化研究

Three organic-inorganic polyoxoniobate-based compounds modified with Cu(II) amine complexes: synthesis, characterization, and catalytic studies for oxidation of styrene.

作者信息

Duan Zhi-Cheng, Li Guanghua, Li Ke-Chang, Cui Xiao-Bing

机构信息

College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, Jilin, 130023, P. R. China.

出版信息

Dalton Trans. 2024 Nov 12;53(44):17880-17892. doi: 10.1039/d4dt02544j.

Abstract

Three novel organic-inorganic polyoxoniobate-based compounds modified with Cu(II) amine complexes were synthesized under hydrothermal conditions with the chemical formulas as follows: K[Cu(enMe)]KSiNbO(VO)·9HO (1), K[Cu(enMe)][KHPNbO(VO)]·12.5HO (2), and K[Cu(enMe)][KHVNbO(VO)]·12.5HO (3) (enMe = 1,2-diaminopropane). These compounds were characterized by single crystal X-ray diffraction, infrared spectroscopy (IR), UV-Vis spectroscopy, elemental analysis and powder X-ray diffraction (PXRD) analysis. Notably, while these three compounds exhibit identical cell parameters, they possess distinct stoichiometric compositions and differing polyoxometalate building block structures. Typically, compounds with the same cell parameters are classified as isostructural, sharing identical structures with only minor elemental variations in their compositions. To the best of our knowledge, compounds 1-3 represent the first instances of compounds that share the same cell parameters yet are not isostructural. In this study, we not only synthesized these three compounds and thoroughly examined the differences in their structures and properties, but also investigated their catalytic performances as catalysts for the oxidation of styrene.

摘要

在水热条件下合成了三种用Cu(II)胺配合物修饰的新型有机-无机聚氧铌酸盐基化合物,其化学式如下:K[Cu(enMe)]KSiNbO(VO)·9H₂O (1)、K[Cu(enMe)][KHPNbO(VO)]·12.5H₂O (2)和K[Cu(enMe)][KHVNbO(VO)]·12.5H₂O (3)(enMe = 1,2-二氨基丙烷)。通过单晶X射线衍射、红外光谱(IR)、紫外-可见光谱、元素分析和粉末X射线衍射(PXRD)分析对这些化合物进行了表征。值得注意的是,虽然这三种化合物表现出相同的晶胞参数,但它们具有不同的化学计量组成和不同的多金属氧酸盐结构单元结构。通常,具有相同晶胞参数的化合物被归类为同构体,仅在其组成上有微小的元素变化时共享相同的结构。据我们所知,化合物1-3代表了具有相同晶胞参数但不是同构体的化合物的首例。在本研究中,我们不仅合成了这三种化合物并深入研究了它们在结构和性质上的差异,还研究了它们作为苯乙烯氧化催化剂的催化性能。

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