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四卤化铀UX（X = Cl、Br、I）/乙酸乙酯体系中溶剂诱导自电离的意外发现。

Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX (X = Cl, Br, I)/Ethyl Acetate System.

作者信息

Deubner H Lars, Graubner Tim, Buchner Magnus R, Weigend Florian, Ivlev Sergei I, Karttunen Antti J, Kraus Florian

机构信息

Philipps-Universität Marburg, Fachbereich Chemie, Hans-Meerwein-Str. 4, Marburg, Hessen 35032, Germany.

Aalto University, Department of Chemistry and Materials Science, Kemistintie 1, Aalto 00076, Finland.

出版信息

ACS Omega. 2022 Apr 1;7(14):11995-12003. doi: 10.1021/acsomega.2c00175. eCollection 2022 Apr 12.

DOI:10.1021/acsomega.2c00175
PMID:35449913
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9016826/
Abstract

The reaction of the uranium(IV) halides UCl, UBr, or UI with ethyl acetate (EtOAc) leads to the formation of the complexes [UX(EtOAc)][UX(EtOAc)] (X = Cl, Br) or [UI(EtOAc)]. Thus, both UCl and UBr show self-ionization in ethyl acetate to a distorted pentagonal bipyramidal [UX(EtOAc)] cation and a distorted octahedral [UX(EtOAc)] anion. Surprisingly, the chloride and bromide compounds are not isotypic. While [UCl(EtOAc)][UCl(EtOAc)] crystallizes in the orthorhombic crystal system, space group 222 at 250 K, the bromide compound crystallizes in the monoclinic crystal system, 12/1 at 100 K. Unexpectedly, UI does not show self-ionization but forms [UI(EtOAc)] molecules, which crystallize in the monoclinic crystal system, 2/, at 100 K. The compounds were characterized by single-crystal X-ray diffraction, IR, Raman, and NMR spectroscopy, as well as molecular quantum chemical calculations using solvent models.

摘要

四价铀卤化物UCl、UBr或UI与乙酸乙酯（EtOAc）反应会生成配合物[UX(EtOAc)][UX(EtOAc)]（X = Cl、Br）或[UI(EtOAc)]。因此，UCl和UBr在乙酸乙酯中都会发生自电离，生成畸变的五角双锥[UX(EtOAc)]阳离子和畸变的八面体[UX(EtOAc)]阴离子。令人惊讶的是，氯化物和溴化物化合物并非同型。[UCl(EtOAc)][UCl(EtOAc)]在250 K时以正交晶系（空间群222）结晶，而溴化物化合物在100 K时以单斜晶系（12/1）结晶。出乎意料的是，UI并不表现出自电离，而是形成[UI(EtOAc)]分子，该分子在100 K时以单斜晶系（2/）结晶。这些化合物通过单晶X射线衍射、红外光谱、拉曼光谱和核磁共振光谱以及使用溶剂模型的分子量子化学计算进行了表征。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/399d/9016826/928f391cdd27/ao2c00175_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/399d/9016826/a1e8291dbeed/ao2c00175_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/399d/9016826/83ef940072d9/ao2c00175_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/399d/9016826/8a213c73df9c/ao2c00175_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/399d/9016826/928f391cdd27/ao2c00175_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/399d/9016826/a1e8291dbeed/ao2c00175_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/399d/9016826/83ef940072d9/ao2c00175_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/399d/9016826/8a213c73df9c/ao2c00175_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/399d/9016826/928f391cdd27/ao2c00175_0003.jpg

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