Reactions in Anhydrous Liquid Ammonia : Syntheses and Crystal Structures of [M(NH3)8]I2 (M = Eu, Yb) with Bicapped Trigonal-Prismatic Octaammine Lanthanoid(II) Cations

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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2020-08-31

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en

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7

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Zeitschrift fur Anorganische und Allgemeine Chemie, Volume 646, issue 16, pp. 1396-1402

Abstract

The compounds [M(NH3)8]I2 (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(NH3)8]X2 (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 S8) 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(NH3)8]2+ cations in the solid state.

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Europium, Liquid ammonia, Quantum-chemical calculations, Structure elucidation, Ytterbium

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Rudel, S S, Graubner, T, Karttunen, A J & Kraus, F 2020, ' Reactions in Anhydrous Liquid Ammonia : Syntheses and Crystal Structures of [M(NH3)8]I2 (M = Eu, Yb) with Bicapped Trigonal-Prismatic Octaammine Lanthanoid(II) Cations ', Zeitschrift fur Anorganische und Allgemeine Chemie, vol. 646, no. 16, pp. 1396-1402 . https://doi.org/10.1002/zaac.202000181