来自液氨溶液反应的氰化铀

IF 2 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry Pub Date : 2024-02-08 DOI:10.1002/ejic.202400041

Tim Graubner, Dr. Stefan S. Rudel, Dr. Sergei I. Ivlev, Prof. Dr. Antti J. Karttunen, Prof. Dr. Florian Kraus

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引用次数: 0

摘要

在液态无水氨中，铀的三卤化物和四卤化物 UBr3、UI3、UCl4 和 UI4 与不同的氰化物 MCN（M = K、Ag）发生反应，生成了三种新型铀（IV）氰化物。UCl4 在 KCN 存在下反应生成化合物 [U(CN)(NH3)8]Cl3∙3NH3、而 UBr3 和 UI3 在 AgCN 存在下被氧化生成化合物 (µ-CN){(H3N)5U(µ-NH2)3U(NH3)5}]Br4∙2NH3 和 (µ-CN){(H3N)5U(µ-NH2)3U(NH3)5}]I4∙2NH3 。UI4 与 KCN 在 aNH3 中反应也生成了化合物 (µ-CN){(H3N)5U(µ-NH2)3U(NH3)5}]I4∙2NH3 。(µ-CN){(H3N)5U(µ-NH2)3U(NH3)5}]X4∙2NH3（X = Br，I）分别在不同的空间群 Pmn21（编号 31）和 Imm2（编号 44）中结晶。在这两种情况下，(µ-CN){(H3N)5U(µ-NH2)3U(NH3)5}]4+阳离子都会形成无限股。我们对观察到的[U(CN)(NH3)8]3+阳离子和[(µ-CN)2{(H3N)5U(µ-NH2)3U(NH3)5}]3+模型阳离子进行了量子化学计算和本征键轨道分析，以深入了解成键情况。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Uranium Cyanides from Reactions in Liquid Ammonia Solution

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Uranium Cyanides from Reactions in Liquid Ammonia Solution

Reactions of uranium tri- and tetrahalides, UBr₃, UI_3, 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 (μ-CN){(H₃N)₅U(μ-NH₂)₃U(NH₃)₅}]Br₄ ⋅ 2NH₃, and (μ-CN){(H₃N)₅U(μ-NH₂)₃U(NH₃)₅}]I₄ ⋅ 2NH₃. The reaction of UI₄ with KCN in aNH₃ also yielded the compound (μ-CN){(H₃N)₅U(μ-NH₂)₃U(NH₃)₅}]I₄ ⋅ 2NH₃. The compounds (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 (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.

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来源期刊

European Journal of Inorganic Chemistry 化学-无机化学与核化学

CiteScore

4.30

自引率

4.30%

发文量

419

审稿时长

1.3 months

期刊介绍： The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry: Chemische Berichte Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.