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Uranyl Complexation by Chloride Ions. Formation of a Tetrachlorouranium(VI) Complex in Room Temperature Ionic Liquids [Bmim][Tf$_2$N] and [MeBu$_3$N][Tf$_2$N]

Abstract : The tetrachlorouranium(VI) complex is formed in [Bmim][Tf2N] and [MeBu3N][Tf2N] from a uranium(VI) solution in the presence of a stoichiometric quantity of chloride ions. The [UVIO2Cl4]2- absorption and emission spectra show bands splitting in comparison with the [UVIO2]2+ spectra, as observed in the solid state, organic solvents, and chloroaluminate-based ionic liquids. The fluorescence lifetime of [UO2Cl4]2- in [MeBu3N][Tf2N] is 0.7 ± 0.1 s. The reduction potential of this complex is -1.44 and -1.8 V vs Ag/Ag+ respectively in [Bmim][Tf2N] and [MeBu3N][Tf2N] and does not depend on the chloride concentration. The mechanism proposed for the redox process is a monoelectronic reduction to form [UVO2Cl4]3-, followed by a chemical reaction. The tetrachlorouranium(V) complex seems more stable in [Bmim][Tf2N] than in [MeBu3N][Tf2N]. The electrochemical analysis put in evidence specific interactions of the ionic liquid cation with the uranium anionic species.
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http://hal.in2p3.fr/in2p3-00128982
Contributor : Dominique Girod <>
Submitted on : Monday, February 5, 2007 - 12:57:03 PM
Last modification on : Wednesday, September 16, 2020 - 4:07:55 PM

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M.-O. Sornein, C. Cannes, C. Le Naour, G. Lagarde, E. Simoni, et al.. Uranyl Complexation by Chloride Ions. Formation of a Tetrachlorouranium(VI) Complex in Room Temperature Ionic Liquids [Bmim][Tf$_2$N] and [MeBu$_3$N][Tf$_2$N]. Inorganic Chemistry, American Chemical Society, 2006, 45, pp.10419 -10421. ⟨10.1021/ic061751q⟩. ⟨in2p3-00128982⟩

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