Speciation of Copper(II) Complexes in an Ionic Liquid Based on Choline Chloride and in Choline Chloride/Water Mixtures

摘要

A deep-eutectic solvent with the properties of an ionic liquid is formed when choline chloride is mixed with copper(II) chloride dihydrate in a 1:2 molar ratio. EXAFS and UV–vis–near-IR optical absorption spectroscopy have been used to compare the coordination sphere of the cupric ion in this ionic liquid with that of the cupric ion in solutions of 0.1 M of CuCl2·2H2O in solvents with varying molar ratios of choline chloride and water. The EXAFS data show that species with three chloride ions and one water molecule coordinated to the cupric ion as well as species with two chloride molecules and two water molecules coordinated to the cupric ion are present in the ionic liquid. On the other hand, a fully hydrated copper(II) ion is formed in an aqueous solution free of choline chloride, and the tetrachlorocuprate(II) complex forms in aqueous choline chloride solutions with more than 50 wt % of choline chloride. In solutions with between 0 and 50 wt % of choline chloride, mixed chloro–aquo complexes occur. Upon standing at room temperature, crystals of CuCl2·2H2O and of Cu(choline)Cl3 formed in the ionic liquid. Cu(choline)Cl3 is the first example of a choline cation coordinating to a transition-metal ion. Crystals of [choline]3[CuCl4][Cl] and of [choline]4[Cu4Cl10O] were also synthesized from molecular or ionic liquid solvents, and their crystal structures were determined.