通过三丁基甲基铵阳离子（MeBu3N(+)）、1-丁基-2,3-二甲基咪唑阳离子（BuMe2Im(+)）和1-丁基-2-甲基咪唑阳离子（BuMeIm(+)）对六氯铀酸根阴离子配合物（UCl6(2-)）进行溶剂化作用。

Solvation of UCl6(2-) anionic complex by MeBu3N(+), BuMe2Im(+), and BuMeIm(+) cations.

作者信息

Bossé Emilie, Den Auwer Christophe, Berthon Claude, Guilbaud Philippe, Grigoriev Mikhail S, Nikitenko Serguei, Le Naour Claire, Cannes Céline, Moisy Philippe

机构信息

CEA Marcoule, DRCP/SCPS, BP 17171, 30207 Bagnols sur Cèze Cedex, France.

出版信息

Inorg Chem. 2008 Jul 7;47(13):5746-55. doi: 10.1021/ic702477z. Epub 2008 Jun 14.

DOI:10.1021/ic702477z

PMID:18553905

Abstract

The complexes [MeBu 3N] 2[UCl 6] and [BuMe 2Im] 2[UCl 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 (+).

摘要

通过单晶X射线衍射、扩展X射线吸收精细结构光谱、电化学、紫外可见吸收光谱和核磁共振等方法，对配合物[MeBu₃N]₂[UCl₆]和[BuMe₂Im]₂[UCl₆]在固态以及在[MeBu₃N][Tf₂N]、[BuMe₂Im][Tf₂N]和[BuMeIm][Tf₂N]室温离子液体溶液中的情况进行了表征。这些技术揭示了在固态和溶液中，UCl₆²⁻配合物与离子液体阳离子之间存在氢键。MeBu₃N⁺阳离子通过氮原子α-碳原子上的质子与UCl₆²⁻相互作用。咪唑环上的质子参与了BuMe₂Im⁺阳离子与UCl₆²⁻阴离子之间的相互作用。对于BuMeIm⁺阳离子，已证实C(2)上酸性最强的质子与UCl₆²⁻的氯原子之间存在主要相互作用。实验结果还表明，UCl₆²⁻阴离子与阳离子之间相互作用的强度随离子液体阳离子的不同而变化，顺序如下：MeBu₃N⁺≈BuMe₂Im⁺ << BuMeIm⁺。