Octachalcogen Cations Te82+, Se82+, and Mixed (Te8-xSex)82+ Stabilized by Chlorometallates of Bi, Zr, and Hf: Synthesis and Crystal Structures of Se8[Bi4Cl14] and E8[MCl6] (E = Se, Te; M = Zr, Hf)
Octachalcogen Cations Te82+, Se82+, and Mixed (Te8-xSex)82+ Stabilized by Chlorometallates of Bi, Zr, and Hf: Synthesis and Crystal Structures of Se8[Bi4Cl14] and E8[MCl6] (E = Se, Te; M = Zr, Hf)
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Bi、Zr 和 Hf 的氯金属盐稳定的八硫属元素阳离子 Te82 、 Se82 和混合 (Te8-xSex)82：Se8[Bi4Cl14] 和 E8[MCl6] 的合成和晶体结构（E = Se、Te；M = Zr，
DOI：
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
T. Hilbert
中科院分区：
文献类型：
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作者：
A. Baumann;J. Beck;T. Hilbert
通过元素硫属元素E（E = Se，Te）与相应的四氯化物ECl 4和刘易斯酸性金属卤化物ZrCl 4、HfCl 4和BiCl 3反应获得标题化合物。另一种方法，特别是用于制备混合Se/Te物质的方法，是通过添加相应的互补硫族元素来扩大E4 MCl 6]（M = Zr，Hf）中的较小阳离子环。所有反应均在密封、抽真空的玻璃安瓿中在120 °C至220 °C的温度下进行，并产生Se 8 [Bi 4Cl 14]、（Te5.0Se3.0）[HfCl 6]、（Te5.3Se2.7）[ZrCl 6]、（Te6.5Se1.5）[ZrCl 6]和Te 8 [HfCl 6]的黑色晶体，其已通过晶体结构分析鉴定。所有五种化合物都含有八元硫族环，其内-外构象与已知的八元硫族化合物E82+（E = S，Se，Te）同构。而在（Te5.0Se3.0）[HfCl6]，（Te5.3Se2.7）[ZrCl6]，（Te6.5Se1.5）[ZrCl 6]和Te 8 [HfCl 6]的分子多阳离子被离散的八面体[MCl 6]2-抗衡离子包围，Se 4 [Bi 4Cl 14]包含由各种顶点和边共享BiCl x多面体（x = 6，7）构建的二维聚合阴离子（[Bi 4Cl 14]2-）n。Bi-Cl键长分布在250和350 μ m之间的宽范围内。
The title compounds were obtained by the reaction of elemental chalcogens E (E = Se, Te) with the respective tetrachlorides ECl4 and the Lewis acidic metal halides ZrCl4, HfCl4, and BiCl3. An alternative way, particularly for the preparation of mixed Se/Te-species, is the enlargement of smaller cationic rings in E4MCl6] (M = Zr, Hf) by adding the respective complementary chalcogen. All reactions were carried out in sealed, evacuated glass ampoules at temperatures between 120 °C and 220 °C, and yielded black crystals of Se8[Bi4Cl14], (Te5.0Se3.0)[HfCl6], (Te5.3 Se2.7)[ZrCl6], (Te6.5Se1.5)[ZrCl6] and Te8[HfCl6], which have been identified by crystal structure analyses. All five compounds contain eight-membered chalcogen rings in an endo-exo-conformation which are isostructural to the known octachalcogen dications E82+ (E = S, Se, Te). While in (Te5 .0Se3.0)[HfCl6], (Te5.3Se2 .7 )[ZrCl6], (Te6 .5Se1.5 )[ZrCl6] and Te8[HfCl6] the molecular polycations are surrounded by discrete, octahedral [MCl6]2- counterions, Se4[Bi4Cl14] contains a two-dimensional polymeric anion ([Bi4Cl14]2-)n built of a variety of vertex and edge-sharing BiClx-polyhedra (x = 6, 7). The Bi-Cl bond lengths are spread over a wide range between 250 and 350 pm.