Reactions of ThX4 (X=F, Cl, Br, I) with Liquid Ammonia-Crystal Structures and a Theoretical Study of Ammine Thorium(IV) Halide Ammoniates

H. Lars Deubner, Tim Graubner, Florian Weigend, Antti J. Karttunen, Florian Kraus*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

Abstract

Reactions of thorium tetrahalides ThX4 (X=Cl, Br, I) with liquid ammonia at room temperature lead to the formation of decaammine thorium(IV) halide ammoniates. Their different compositions [Th(NH3)10]X4 ⋅ nNH3 were established by single crystal X-ray diffraction. While for the chloride the formation of a tetraammoniate is observed, the reaction of the bromide leads to an octaammoniate, whereas the iodide results in approximately a nonaammoniate. Additionally, the formation of the dinuclear Th complex compound [Th2Cl2(NH3)14(μ-O)]Cl4 ⋅ 3NH3 was observed when moisture was present within NH3. As expected, the Th and the previously reported U compounds [An(NH3)10]Br4 ⋅ 8NH3 (Pbca, An=Th, U), [An(NH3)10]I4 ⋅ 9NH3 (P4/n), and [An2Cl2(NH3)14(μ-O)]Cl4 ⋅ 3NH3 (P (Formula presented.)) are isotypic, respectively. Surprisingly, ThCl4 formed the decaammine complex [Th(NH3)10]Cl4 ⋅ 4NH3 (P121/n1), while UCl4 formed the octaammine chlorido complex [UCl(NH3)8]Cl3 ⋅ 3NH3 (Pnma) in ammonia. Quantum-chemical gas-phase calculations were carried out to study the molecular structures and the energetics of the complex cations. In addition, the localized molecular orbitals (LMO) and Intrinsic Bonding Orbitals (IBO) were analyzed. However, the calculations could not explain the preferred formation of the [Th(NH3)10]4+ complex over the hypothetical cation [ThCl(NH3)8]3+.

Original languageEnglish
Pages (from-to)2787-2796
JournalEuropean Journal of Inorganic Chemistry
Volume2021
Issue number27
Early online date22 Jun 2021
DOIs
Publication statusPublished - 22 Jul 2021
MoE publication typeA1 Journal article-refereed

Keywords

  • Ammonia
  • Complex
  • Crystal structure
  • Halide
  • Thorium

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