Cation‐Dependent Nuclearity of New HomolepticAzidocuprates(II), From Discrete Ions toAnionic Strands and Sheets

M. Köckerling, Alexander Hinz
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Abstract

In chemical reactions of copper(II) acetate dihydrate with imidazolium azide salts in ethanol solution several new homoleptic azidocuprates(II) were obtained. In dependency of the used counter cation various different azidocuprate moieties were crystalized. The doubly charged DMMDIm2+ cation facilitates the formation of mononuclear [Cu(N3)4]2– complex anions, while the utilisation of the (PeMIm)+ ion enables the isolation of a di‐nuclear [Cu2(N3)6]2– salt. By using the unsymmetrical imidazolium ions (BMIm)+ or (EMIm)+ salts with the tri‐nuclear [Cu3(N3)8]2– complex anion are obtained. With the (DML)+ cation an azidocuprate(II) crystallizes , which contains both [Cu(N3)4]2– and the [Cu2(N3)6]2– anion. The anions in the salt with the (PeMIm)+ cation are interconnected through further Cu−N bonds and form layers with a 2D‐honecomb structure. The tri‐nuclear units in the (BMIm)+ and the (EMIm)+salts form coordination strands of different structures.
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从离散离子到阴离子链和阴离子片,新均质叠氮(II)的阳离子依赖性核性
在乙醇溶液中,二水醋酸铜(II)与叠氮化咪唑盐发生化学反应,得到了几种新的均叠氮铜酸盐(II)。根据所用反阳离子的不同,结晶出了各种不同的叠氮基杯酸盐分子。带双电荷的 DMMDIm2+ 阳离子有助于形成单核[Cu(N3)4]2- 复阴离子,而利用(PeMIm)+ 离子则可以分离出双核[Cu2(N3)6]2- 盐。通过使用不对称咪唑离子 (BMIm)+ 或 (EMIm)+ 盐与三核[Cu3(N3)8]2-络阴离子结合,可以得到三核[Cu3(N3)8]2-盐。在(DML)+阳离子的作用下,会结晶出叠氮琥珀酸盐(II),其中同时含有[Cu(N3)4]2-和[Cu2(N3)6]2-阴离子。带有(PeMIm)+阳离子的盐中的阴离子通过更多的 Cu-N 键相互连接,形成具有二维-昂子结构的层。(BMIm)+和(EMIm)+盐中的三核单元形成了不同结构的配位层。
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