Coordination environment of [UO2Br4](2-) in ionic liquids and crystal structure of [Bmim](2)[UO2Br4]

M.O. Sornein, M. Mendes, C. Cannes, C. Le Naour, Peter Nockemann, K. Van Hecke, L. Van Meervelt, J.C. Berthet, C. Hennig

Research output: Contribution to journalArticlepeer-review

25 Citations (Scopus)

Abstract

The complex formed by the reaction of the uranyl ion, UO22+, with bromide ions in the ionic liquids 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmiml[Tf2N]) and methyl-tributylammonium bis(trifluoromethylsulfonyl)imide ([MeBu3N][Tf2N]) has been investigated by UV-Vis and U L-III-edge EXAFS spectroscopy and compared to the crystal structure of [Bmim](2)[UO2Br4]. The solid state reveals a classical tetragonal bipyramid geometry for [UO2Br4](2-) with hydrogen bonds between the Bmim(+) and the coordinated bromides. The UV-Vis spectroscopy reveals the quantitative formation of [UO2Br4](2-) when a stoichiometric amount of bromide ions is added to UO2(CF3SO3)(2) in both Tf2N-based ionic liquids. The absorption spectrum also suggests a D-4h symmetry for [UO2Br4](2-) in ionic liquids, as previously observed for the [UO2Cl4](2-) congener. EXAFS analysis supports this conclusion and demonstrates that the [UO2Br4](2-) coordination polyhedron is maintained in the ionic liquids without any coordinating solvent or water molecules. The mean U-O and U-Br distances in the solutions, determined by EXAFS, are, respectively, 1.766(2) and 2.821(2)angstrom in [Bmim][Tf2N], and, respectively, 1.768(2) and 2.827(2) angstrom, in [MeBu3N][Tf2N]. Similar results are obtained in both ionic liquids indicating no significant influence of the ionic liquid cation either on the complexation reaction or on the structure of the uranyl species. (C) 2009 Elsevier Ltd. All rights reserved.
Original languageEnglish
Pages (from-to)1281-1286
Number of pages6
JournalPolyhedron
Volume28
Issue number7
DOIs
Publication statusPublished - 12 May 2009

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

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