Uranium Cyanides from Reactions in Liquid Ammonia Solution

Loading...
Thumbnail Image
Access rights
openAccess
Journal Title
Journal ISSN
Volume Title
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Date
2024-06-03
Major/Subject
Mcode
Degree programme
Language
en
Pages
10
Series
European Journal of Inorganic Chemistry, Volume 27, issue 16
Abstract
Reactions of uranium tri- and tetrahalides, UBr3, UI3, UCl4, and UI4, with different cyanides MCN (M=K, Ag) in liquid anhydrous ammonia led to three novel uranium(IV) cyanide compounds. The reaction of UCl4 in the presence of KCN resulted in the compound [U(CN)(NH3)8]Cl3 ⋅ 3NH3, while UBr3 and UI3 were oxidized in the presence of AgCN to form the compounds (Formula presented.) (μ-CN){(H3N)5U(μ-NH2)3U(NH3)5}]Br4 ⋅ 2NH3, and (Formula presented.) (μ-CN){(H3N)5U(μ-NH2)3U(NH3)5}]I4 ⋅ 2NH3. The reaction of UI4 with KCN in aNH3 also yielded the compound (Formula presented.) (μ-CN){(H3N)5U(μ-NH2)3U(NH3)5}]I4 ⋅ 2NH3. The compounds (Formula presented.) (μ-CN){(H3N)5U(μ-NH2)3U(NH3)5}]X4 ⋅ 2NH3 (X=Br, I) crystallize in different space groups, Pmn21 (no. 31) and Imm2 (no. 44), respectively. In both cases, the (Formula presented.) (μ-CN){(H3N)5U(μ-NH2)3U(NH3)5}]4+ cation forms infinite strands. We conducted quantum-chemical calculations and Intrinsic Bond Orbital analyses on the observed [U(CN)(NH3)8]3+ cation and the [(μ-CN)2{(H3N)5U(μ-NH2)3U(NH3)5}]3+ model cation to gain insight into the bonding situation.
Description
Publisher Copyright: © 2024 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.
Keywords
cyanide, liquid ammonia, quantum-chemical calculation, Uranium
Other note
Citation
Graubner, T, Rudel, S S, Ivlev, S I, Karttunen, A J & Kraus, F 2024, ' Uranium Cyanides from Reactions in Liquid Ammonia Solution ', European Journal of Inorganic Chemistry, vol. 27, no. 16, e202400041 . https://doi.org/10.1002/ejic.202400041