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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Reactions in Anhydrous Liquid Ammonia: Syntheses and Crystal Structures of [M(NH_3)_8]I_2 (M = Eu, Yb) with Bicapped Trigonal- Prismatic Octaammine Lanthanoid(II) Cations
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Reactions in Anhydrous Liquid Ammonia: Syntheses and Crystal Structures of [M(NH_3)_8]I_2 (M = Eu, Yb) with Bicapped Trigonal- Prismatic Octaammine Lanthanoid(II) Cations

机译：无水液氨中的反应：用偏排的三角形 - 棱柱形辛酸镧（II）阳离子的[M（NH_3）_8] I_2（M = EU，YB）的合成和晶体结构

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摘要

The compounds [M(NH_3)_8]I_2 (M = Eu, Yb) were obtained from reactions in anhydrous liquid ammonia solutions as side products. They were characterized by single-crystal X-ray diffraction and found to be isotypic to the compounds [Ca(NH_3)_8]X_2 (X = Cl, Br, I). The coordination sphere of the lanthanoid(II) cations is not square-antiprismatic but much better described as bicapped trigonal-prismatic. In contrast, quantum-chemical gas-phase calculations show the square-antiprismatic coordination polyhedron (point group S_8) to be energetically favored over the bicapped trigonal prism and the latter is not even a true local minimum. Obviously, hydrogen bonding and eventually other weak interactions have an impact on the observed bicapped trigonal- prismatic coordination sphere of the [M(NH_3)_8]~(2+) cations in the solid state.
机译：化合物[M（NH_3）_8]I_2（M=Eu，Yb）是作为副产物在无水液氨溶液中反应得到的。通过单晶X射线衍射对它们进行了表征，发现它们与化合物[Ca（NH_3）_8]X_2（X=Cl，Br，I）具有同型性。镧系（II）阳离子的配位球不是方形的反棱柱体，而是更好地描述为双帽三角棱柱体。相比之下，量子化学气相计算表明，正方形反棱柱配位多面体（点群S_8）在能量上优于双帽三角棱镜，后者甚至不是真正的局部极小值。显然，氢键和其他弱相互作用对固态[M（NH_3）_8]~（2+）阳离子的双帽三角棱镜配位球有影响。

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