title: Reaction mechanism of Cl2 and 1-alkyl-3-methylimidazolium chloride ionic liquids.
abstract: Systems containing 1-alkyl-3-methylimidazolium chloride ionic liquid and chlorine gas were investigated. Using relativistic density functional theory, we calculated the formation mechanism of trichloride and hydrogen dichloride anions in an Emim(+)Cl(-) + Cl(2) system. Emim(+)Cl(3)(-) forms without energy barriers. The more stable species ClEmim(+)HCl(2)(-) forms through chlorine substitution. Substitution of a H on the imidazolium ring is much easier than substitution on the alkyl side chains. Infrared, Raman, ESI-MS, and (1)H NMR spectra were measured for EmimCl, BmimCl, and DmimCl with and without Cl(2) gas. The coexistence of Cl(3)(-) and HCl(2)(-), as well as chlorine-substituted cations, was confirmed by detection of their spectroscopic signals in the Cl(2) added ionic liquids. Cl substitution appears less serious for cations with longer side chains.
authors: Beijing National Laboratory for Molecular Sciences, Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science, College of Chemistry and Molecular Engineering, Peking University, Beijing, China. swhu@pku.edu.cn
authors: Shao-Wen
authors: SW
authors: Hu
authors: Zhu-Xiang
authors: ZX
authors: Wang
authors: Feng
authors: F
authors: Qu
authors: Tai-Wei
authors: TW
authors: Chu
authors: Xiang-Yun
authors: XY
authors: Wang
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D007093:Imidazoles / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry*
chemical_list: C544334:1-allyl-3-methylimidazolium; D000498:Allyl Compounds; D002712:Chlorides; D007093:Imidazoles; D052578:Ionic Liquids