Solubility Behaviour of TiCl₄, ZrCl₄, and HfCl₄ in Chloroaluminate Ionic Liquids

Abstract

The solubility of NbCl 5 , TaCl 5 , TiCl 4 , ZrCl 4 , and HfCl 4 in neutral [BMIM][AlCl 4 ] (BMIM = 1-butyl-3-methylimidazolium) was determined. While TiCl 4 was immiscible with the neutral ionic liquid, 0.80 molar equivalents of ZrCl 4 and stoichiometric amounts of HfCl 4 dissolved in the melt at ambient temperature. The crystal structures and the unit cell parameters of [BMIM]

New Ternary Hafniumhalides: Cs[Hf2Br9] and Rb[Hf2Br9]

“…Comparable dinuclear metal halogenido complex anions are found in (PhMe 3 N)[Hf 2 Cl 9 ],4 (TeBr 3 )[Zr 2 Br 9 ],12 and [Zr(Me 2 SiO) 6 Br 2 ]‐[Zr 2 Br 9 ] (Ph = phenyl, Me = methyl) 8. The atom distances for the same type of distances of the zirconium bromides compare well with the values of the title compounds.…”

“…Preparations and properties of different mono‐ and polynuclear compounds have been reported 2–5. In general, these compounds are prepared by dissolving a metal tetrahalide in an organic solvent5,6 or ionic liquid4 in the presence of an organic cation. Compounds with [ M 2 X 9 ] – ‐ or [ M 2 X 10 ] 2– anions ( M = Ti, Zr, or Hf, and X = Cl, Br, or I) are reported in the literature 7–12…”

Structures, properties and applications of bimetallic composite ionic liquids

“…Dötterl等 [35] NbCl5的溶解比不超过0.2, TiCl4则完全不溶. Kore等 [16] 发现室温下ZnCl2 在 Et3NHCl-xAlCl3 中仅Et3NHCl-0.5AlCl3-0.5ZnCl2配比时能以均相离子液体形式存在.…”

Crystallographic Insights into the Behavior of Highly Acidic Metal Cations in Ionic Liquids from Reactions of Titanium Tetrachloride with [1-Butyl-3-Methylimidazolium][X] Ionic Liquids (X = Chloride, Bromide, Tetrafluoroborate)

“…Our observation that TiCl4 and [C4mim]Cl gave a sticky solid reaction mixture conflicted with prior reports that this reaction should give a room temperature liquid 58 or that pure [C4mim]2[Ti2Cl10] was a crystalline solid. 39 In order to avoid supercooling, we also attempted 1:1 molar reactions of TiCl4 at room temperature using hand grinding in an agate mortar and pestle to drive the reaction, which led to homogeneous yet amorphous solid powders (see Figure S3) Figure S4). Overall, the amorphous solids obtained in this study appear to show exceptional stability, although prior reports of the isolation of crystalline complexes with these compositions, 40,41 suggest they should be metastable with respect to the crystalline complexes.…”

“…11,23 In addition to the well-studied [AlCl4]systems, 24 crystal structures are known for chlorometallates of trivalent Au, 25,26 Bi, 27 Ce, 28,29 Dy, 30 Er, 30,31 Eu, 30,32 Fe, 33,34,35 Gd, 32 La, 36,37 Nd, 32 Pr, 32 Sb, 38 Sc, 29 Sm, 32, Y, 29 and Yb. 30 However, for tetravalent metal ions, the list is restricted to just Ge, 16 Ir, 25 Pt, 25 Sn, 22 Ti, 39,40,41 U, 42 V, 43 and Zr, 11,39,44,45,46 for pentavalent ions only Np, 47 and Nb, 48,49 and for hexavalent ions only U 50 and Mo. 51,52 This may reflect how the weakly coordinating ions found in many commonly used ILs cannot dissolve salts of highly charged ions.…”