期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 21, 期 23, 页码 8324-8335出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201500239
关键词
conductivity; imidazolium salts; ion pairs; ionic liquids; solutions
资金
- CNPq
- CAPES
- FAPERGS (Brazil)
- DFG [SPP 1191]
- DFG Collaborative Research Center [SFB 652]
The formation, stabilisation and reactivity of contact ion pairs of non-protic imidazolium ionic liquids (ILs) in solution are conceptualized in light of selected experimental evidence as well theoretical calculations reported mainly in the last ten years. Electric conductivity, NMR, ESI-MS and IR data as well as theoretical calculations support not only the formation of contact ion pairs in solution, but also the presence of larger ionic and neutral aggregates even when dissolved in solvents with relatively high dielectric constants, such as acetonitrile and DMSO. The presence of larger imidazolium supramolecular aggregates is favoured at higher salt concentrations in solvents of low dielectric constant for ILs that contain shorter N-alkyl side chains associated with anions of low coordination ability. The stability and reactivity of neutral contact species are also dependent on the nature of the anion, imidazolium substituents, and are more abundant in ILs containing strong coordinating anions, in particular those that can form charge transfer complexes with the imidazolium cation. Finally, some ILs display reactivities as contact ion pairs rather than solvent-separated ions.
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