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

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Volume Title

A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Date

2021-07-22

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en

Pages

2787-2796

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European Journal of Inorganic Chemistry, Volume 2021, issue 27

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+.

Description

Supplementary data not published with Aalto affiliation. Funding Information: We thank the Deutsche Forschungsgemeinschaft for funding and Dr. Matthias Müller for helping with the single crystal measurement on [Th(NH)]Cl ⋅ 4NH. We thank Dr. Matthias Conrad for helpful discussions. A.J.K. thanks CSC, the Finnish IT Center for Science for computational resources Open access funding enabled and organized by Projekt DEAL. 3 10 4 3 Publisher Copyright: © 2021 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH

Keywords

Ammonia, Complex, Crystal structure, Halide, Thorium

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Citation

Deubner, H L, Graubner, T, Weigend, F, Karttunen, A J & Kraus, F 2021, ' Reactions of ThX 4 (X=F, Cl, Br, I) with Liquid Ammonia-Crystal Structures and a Theoretical Study of Ammine Thorium(IV) Halide Ammoniates ', European Journal of Inorganic Chemistry, vol. 2021, no. 27, pp. 2787-2796 . https://doi.org/10.1002/ejic.202100383