Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX 4 (X = Cl, Br, I)/Ethyl Acetate System

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) ] catio...

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Bibliographic Details
Published in:ACS omega 2022-04, Vol.7 (14), p.11995-12003
Main Authors: Deubner, H Lars, Graubner, Tim, Buchner, Magnus R, Weigend, Florian, Ivlev, Sergei I, Karttunen, Antti J, Kraus, Florian
Format: Article
Language:English
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Summary: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 2 2 2 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.
ISSN:2470-1343
2470-1343
DOI:10.1021/acsomega.2c00175