路易斯酸碱合成[Se3Cl3]2[SnCl6]和[BMIm]2[Ga8As6Cl16O14]

Claus Feldmann, Maxime A. Bonnin, Michael D. Suedes
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引用次数: 0

摘要

[Se3Cl3]2[SnCl6](1)和[BMIm]2[Ga8As6Cl16O14](2)是通过 SnCl2 与 SeCl4 以及 As2O3 与 GaCl3/[BMIm]Cl 在室温和 60 °C 下的路易斯酸碱反应制备的。1 含有一个 Se3 单元的 [ClSe-Se-SeCl2]+ 阳离子和孤立的八面体 [SnCl6]2- 阴离子。该阳离子只能通过在液态二氧化硫中与 AsF5 进行 Se0/Se4+ 合成反应来获得。2 中的[Ga8As6Cl16O14]2-阴离子由两个中心共边的 GaO6 八面体组成,周围环绕着假四面体 AsO3 单元以及四面体 GaCl3O 和 GaCl2O2 单元。此外,一个由六个 GaAs2O3 环包围的近乎平面的中央 Ga4O4 环也是该化合物的特征,而这在以前是没有描述过的。标题化合物的特征是基于单晶和粉末的 X 射线衍射、红外光谱、热重法和光学光谱。
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Lewis‐Acid‐Base Synthesis of [Se3Cl3]2[SnCl6] and [BMIm]2[Ga8As6Cl16O14]
[Se3Cl3]2[SnCl6] (1) and [BMIm]2[Ga8As6Cl16O14] (2) are prepared by Lewis‐acid‐base reaction of SnCl2 with SeCl4 and As2O3 with GaCl3/[BMIm]Cl at room temperature and at 60 °C. 1 contains [ClSe–Se–SeCl2]+ cations with an Se3 unit and isolated octahedral [SnCl6]2– anions. The cation was yet only obtainable via Se0/Se4+ synproportionation in liquid SO2 with AsF5. The [Ga8As6Cl16O14]2– anion in 2 consists of two central edge‐sharing GaO6 octahedra, surrounded by pseudo‐tetrahedral AsO3 units and tetrahedral GaCl3O and GaCl2O2 units. Moreover, an almost planar central Ga4O4 ring surrounded by six GaAs2O3 rings is characteristic, which was not described before. The title compounds are characterized by X‐ray diffraction based on single crystals and powders, infrared spectroscopy, thermogravimetry, and optical spectroscopy.
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