Université de Lyon, Institut de Chimie de Lyon, UMR 5265 CNRS-Université de Lyon-ESCPE Lyon, LC2P2, Equipe COMS, ESCPE 43 Boulevard du 11 Novembre 1918, 69616, Villeurbanne, France.
Dalton Trans. 2010 Feb 7;39(5):1379-88. doi: 10.1039/b919094e. Epub 2009 Dec 1.
Dialkylimidazolium chlorometallate molten salts resulting from the combination of zirconium or hafnium tetrachloride and 1-butyl-3-methylimidazolium chloride, [C(1)C(4)Im][Cl], have been prepared with a molar fraction of MCl(4), R = n(MCl4)/n(MCl4) + n([C1C4IM][Cl]) equal to 0, 0.1, 0.2, 0.33, 0.5, 0.67. The structure and composition were studied by Differential Scanning Calorimetry (DSC), (35)Cl (263 to 333 K), (1)H and (13)C solid state and solution NMR spectroscopy, and electrospray ionisation (ESI) mass spectrometry. The primary anions of the MCl(4)-based ILs were [MCl(5)], [MCl(6)] and [M(2)Cl(9)], whose relative abundances varied with R. For R = 0.33, pure solid C(1)C(4)Im[MCl(6)], for both M = Zr and Hf are formed (m.p. = 366 and 385 K, respectively). For R = 0.67 pure ionic liquids [C(1)C(4)Im][M(2)Cl(9)] for both M = Zr and Hf are formed (T(g) = 224 and 220 K, respectively). The thermal dissociation has been attempted of C(1)C(4)Im[HfCl(6)], and C(1)C(4)Im[ZrCl(6)] monitored by (35)Cl and (91)Zr solid NMR (high temperature up to 551 K).
由四氯化锆或四氯化铪与 1-丁基-3-甲基咪唑氯化物[C(1)C(4)Im][Cl]组合而成的二烷基咪唑鎓氯金属酸盐熔融盐，[MCl(4)]摩尔分数，R=n（MCl4）/n（MCl4）+n[C1C4IM][Cl]等于 0、0.1、0.2、0.33、0.5、0.67，已经制备出来。通过差示扫描量热法（DSC）、（35）Cl（263 至 333 K）、（1）H 和（13）C 固态和溶液 NMR 光谱以及电喷雾电离（ESI）质谱研究了其结构和组成。基于 MCl(4)的 IL 的主要阴离子为[MCl(5)]、[MCl(6)]和[M(2)Cl(9)]，其相对丰度随 R 而变化。对于 R=0.33，形成了纯固态C(1)C(4)Im[MCl(6)]，对于 M=Zr 和 Hf 都是如此（熔点分别为 366 和 385 K）。对于 R=0.67，形成了纯离子液体[C(1)C(4)Im][M(2)Cl(9)]，对于 M=Zr 和 Hf 都是如此（T(g)=224 和 220 K，分别）。通过（35）Cl 和（91）Zr 固态 NMR（高温高达 551 K）监测C(1)C(4)Im[HfCl(6)]和C(1)C(4)Im[ZrCl(6)]的热分解。
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