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Speciation of copper(II) complexes in an ionic liquid based on choline chloride and in choline chloride/water mixtures

Peter De Vreese, Neil R Brooks, Kristof Van Hecke UGent, Luc Van Meervelt, Edward Matthijs, Koen Binnemans and Rik Van Deun UGent (2012) INORGANIC CHEMISTRY. 51(9). p.4972-4981
abstract
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.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
METAL-IONS, DEEP EUTECTIC SOLVENTS, AQUEOUS-SOLUTIONS, CRYSTAL-STRUCTURE, COORDINATION, SALTS, WATER, ELECTRODEPOSITION, SPECTROSCOPY, SYSTEM
journal title
INORGANIC CHEMISTRY
Inorg. Chem.
volume
51
issue
9
pages
4972 - 4981
Web of Science type
Article
Web of Science id
000303952900019
JCR category
CHEMISTRY, INORGANIC & NUCLEAR
JCR impact factor
4.593 (2012)
JCR rank
5/43 (2012)
JCR quartile
1 (2012)
ISSN
0020-1669
DOI
10.1021/ic202341m
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
2118155
handle
http://hdl.handle.net/1854/LU-2118155
date created
2012-05-29 16:33:12
date last changed
2018-01-29 12:12:32
@article{2118155,
  abstract     = {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\ensuremath{-}vis\ensuremath{-}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{\textperiodcentered}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\ensuremath{-}aquo complexes occur. Upon standing at room temperature, crystals of CuCl2{\textperiodcentered}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.},
  author       = {De Vreese, Peter and Brooks, Neil R and Van Hecke, Kristof and Van Meervelt, Luc and Matthijs, Edward and Binnemans, Koen  and Van Deun, Rik},
  issn         = {0020-1669},
  journal      = {INORGANIC CHEMISTRY},
  keyword      = {METAL-IONS,DEEP EUTECTIC SOLVENTS,AQUEOUS-SOLUTIONS,CRYSTAL-STRUCTURE,COORDINATION,SALTS,WATER,ELECTRODEPOSITION,SPECTROSCOPY,SYSTEM},
  language     = {eng},
  number       = {9},
  pages        = {4972--4981},
  title        = {Speciation of copper(II) complexes in an ionic liquid based on choline chloride and in choline chloride/water mixtures},
  url          = {http://dx.doi.org/10.1021/ic202341m},
  volume       = {51},
  year         = {2012},
}

Chicago
De Vreese, Peter, Neil R Brooks, Kristof Van Hecke, Luc Van Meervelt, Edward Matthijs, Koen Binnemans, and Rik Van Deun. 2012. “Speciation of copper(II) Complexes in an Ionic Liquid Based on Choline Chloride and in Choline Chloride/water Mixtures.” Inorganic Chemistry 51 (9): 4972–4981.
APA
De Vreese, P., Brooks, N. R., Van Hecke, K., Van Meervelt, L., Matthijs, E., Binnemans, K., & Van Deun, R. (2012). Speciation of copper(II) complexes in an ionic liquid based on choline chloride and in choline chloride/water mixtures. INORGANIC CHEMISTRY, 51(9), 4972–4981.
Vancouver
1.
De Vreese P, Brooks NR, Van Hecke K, Van Meervelt L, Matthijs E, Binnemans K, et al. Speciation of copper(II) complexes in an ionic liquid based on choline chloride and in choline chloride/water mixtures. INORGANIC CHEMISTRY. 2012;51(9):4972–81.
MLA
De Vreese, Peter, Neil R Brooks, Kristof Van Hecke, et al. “Speciation of copper(II) Complexes in an Ionic Liquid Based on Choline Chloride and in Choline Chloride/water Mixtures.” INORGANIC CHEMISTRY 51.9 (2012): 4972–4981. Print.