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Cs(8)Ga(11)，一种二元镓化合物中的新型孤立簇。价态类似物A(8)Tr(11)X家族：A = Cs、Rb；Tr = Ga、In、Tl；X = Cl、Br、I。

Cs(8)Ga(11), a New Isolated Cluster in a Binary Gallium Compound. A Family of Valence Analogues A(8)Tr(11)X: A = Cs, Rb; Tr = Ga, In, Tl; X = Cl, Br, I.

作者信息

Henning Robert W., Corbett John D.

机构信息

Department of Chemistry and Ames Laboratory-DOE,(1) Iowa State University, Ames, Iowa 50011.

出版信息

Inorg Chem. 1997 Dec 17;36(26):6045-6049. doi: 10.1021/ic970904u.

DOI:10.1021/ic970904u
PMID:11670238
Abstract

Fusion of the elements, and alkali-metal halide when appropriate, in stoichiometric amounts in Ta containers followed by slow cooling results in high yields of the title compounds. X-ray structures refined for rhombohedral Cs(8)Ga(11) (R&thremacr;c, Z = 6, a = 9.9962(5) Å, c = 50.839(6) Å) and Cs(8)Ga(11)Cl (R&thremacr;&thremacr;c, Z = 6, a = 10.0111(7) Å, c = 50.504(6) Å) reveal isolated clusters of pentacapped, trigonal prismatic gallium anions, Ga(11)(7)(-), the former compound being isostructural with K(8)In(11) and A(8)Tl(11) (A = K, Rb, Cs). The clusters are arranged in pseudo-ccp layers separated by double layers of cesium atoms. The halide in Cs(8)Ga(11)Cl is bound in a preformed cavity within the cesium double layers where it is surrounded by eight cations. Of the nine examples reported for A(8)Tr(11)X, three chlorides occur in systems in which the binary A(8)Tr(11) do not form, Rb-Ga, Rb-In, and Cs-In. These halides are the first examples of Tr(11)(7)(-) compounds that are valence phases and do not contain an extra alkali-metal cation and electron. Magnetic susceptibility data indicate an apparently localized electron in paramagnetic Cs(8)Ga(11) and diamagnetism for Cs(8)Ga(11)Cl.

摘要

将各元素以及适量的碱金属卤化物按化学计量比在钽容器中熔融，随后缓慢冷却，可得到高产率的标题化合物。对菱面体Cs(8)Ga(11)（R&thremacr;c，Z = 6，a = 9.9962(5) Å，c = 50.839(6) Å）和Cs(8)Ga(11)Cl（R&thremacr;&thremacr;c，Z = 6，a = 10.0111(7) Å，c = 50.504(6) Å）进行X射线结构精修，结果显示存在孤立的五帽三角棱柱形镓阴离子簇Ga(11)(7)(-)，前一种化合物与K(8)In(11)和A(8)Tl(11)（A = K、Rb、Cs）同构。这些簇排列在由铯原子双层分隔的伪立方密堆积层中。Cs(8)Ga(11)Cl中的卤化物结合在铯双层内预先形成的空腔中，被八个阳离子包围。在报道的九个A(8)Tr(11)X实例中，有三种氯化物出现在二元A(8)Tr(11)不形成的体系中，即Rb - Ga、Rb - In和Cs - In。这些卤化物是Tr(11)(7)(-)化合物的首个实例，它们是价态相，不包含额外的碱金属阳离子和电子。磁化率数据表明，顺磁性Cs(8)Ga(11)中存在明显局域化的电子，而Cs(8)Ga(11)Cl具有抗磁性。

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