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Correlations between the Structures of Binuclear Copper(II) Tetracarboxylates with 1,4-Dioxane and the Nature of Substituent R in the Carboxylate Anion
Russian Journal of Coordination Chemistry ( IF 1.9 ) Pub Date : 2021-07-08 , DOI: 10.1134/s1070328421060087
M. A. Uvarova 1 , S. E. Nefedov 1
Affiliation  

Abstract

The dissolution of aqueous copper(II) acetate in coordinating bidentate 1,4-dioxane (reflux) affords anhydrous mononuclear complex Cu2(µ-OOCMe)4(dioxane)2 (I) (Cu…Cu 2.5781(3) Å). The crystal of complex I contains contacts of the α-H atom of the CH2 fragments of coordinated dioxane with the oxygen atom of the bridging anion with the formation of the 2D metal-organic framework (MOF). The anionic exchange reactions of the acetate bridges by pivalate or trifluoroacetate groups with the corresponding acids in boiling dioxane give 1D MOF {Cu2(µ-OOCR)4(dioxane)}n (R = tBu (II), Cu…Cu 2.5493(7) Å; CF3 (III), Cu…Cu 2.6391(12) Å) characterized by the step and linear geometry, respectively. A similar reaction of Cu2(µ-OOCMe)4(OH2)2 with HOOCCF3 but at room temperature in the presence of crude benzene affords mononuclear complex Cu(OOCCF3)2(OH2)3·2 dioxane (IV). Complexes IIV are studied by elemental and X-ray diffraction analyses (CIF files CCDC nos. 2052618 (I), 2052619 (II), 2052620 (III), and 2052617 (IV)). The influence of the electronic and steric factors of substituents R on the compositions and structures of the mononuclear complexes and MOFs with 1,4-dioxane are discussed for the synthesized and known copper(II) tetracarboxylates.



中文翻译:

含 1,4-二恶烷的双核四羧酸铜 (II) 结构与羧酸根阴离子中取代基 R 的性质之间的相关性

摘要

醋酸铜 (II) 水溶液在配位双齿 1,4-二恶烷(回流)中的溶解提供无水单核络合物 Cu 2 (μ-OOCMe) 4 (二恶烷) 2 ( I ) (Cu…Cu 2.5781(3) Å)。配合物I的晶体包含配位二恶烷CH 2碎片的 α-H 原子与桥接阴离子的氧原子的接触,形成二维金属有机骨架 (MOF)。新戊酸酯或三氟乙酸酯基团与相应酸在沸腾的二恶烷中的乙酸酯桥的阴离子交换反应得到 1D MOF {Cu 2 (µ-OOCR) 4 (二恶烷)} n (R = t Bu (II ), Cu…Cu 2.5493(7) Å; CF 3 ( III ), Cu…Cu 2.6391(12) Å) 分别具有阶梯和线性几何特征。Cu 2 (μ-OOCMe) 4 (OH 2 ) 2与HOOCCF 3的类似反应,但在室温下在粗苯存在下得到单核配合物Cu(OOCCF 3 ) 2 (OH 2 ) 3 ·2 二恶烷( IV ) . 配合- IV(CIF文件CCDC号2052618(通过元素和X射线衍射分析研究了),2052619(II),2052620(III ) 和 2052617 ( IV ))。讨论了取代基 R 的电子和空间因子对合成和已知的四羧酸铜 (II) 的单核配合物和 MOF 与 1,4-二氧六环的组成和结构的影响。

更新日期:2021-07-08
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