Solvation of UCl6(2-) anionic complex by MeBu3N(+), BuMe2Im(+), and BuMeIm(+) cations |
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Authors: | Bossé Emilie Den Auwer Christophe Berthon Claude Guilbaud Philippe Grigoriev Mikhail S Nikitenko Serguei Le Naour Claire Cannes Céline Moisy Philippe |
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Institution: | CEA Marcoule, DRCP/SCPS, BP 17171, 30207 Bagnols sur Cèze Cedex, France. |
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Abstract: | The complexes MeBu 3N] 2UCl 6] and BuMe 2Im] 2UCl 6] were characterized in the solid state and in solution of MeBu 3N]Tf 2N], BuMe 2Im]Tf 2N], and BuMeIm]Tf 2N] room-temperature ionic liquids using single-crystal XRD, EXAFS, electrochemistry, UV-visible absorption spectroscopy, and NMR. In the solid state and in solution, the existence of hydrogen bonding between the UCl 6 (2-) complex and the ionic liquid cations was revealed by these techniques. The MeBu 3N (+) cation interacts with UCl 6 (2-) via the protons on the alpha-carbon atoms of nitrogen. The protons of the imidazolium ring account for the interaction between the BuMe 2Im (+) cation and the UCl 6 (2-) anion. For the BuMeIm (+) cation the major interaction was confirmed between the most acidic proton on C(2) and the chlorides of UCl 6 (2-). The experimental results also show that the intensity of the interaction between the UCl 6 (2-) anion and the cation varies with the ionic liquid cation in the following order: MeBu 3N (+) approximately BuMe 2Im (+) < BuMeIm (+). |
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