Coordination environment of highly concentrated solutions of Cu(II) in ionic liquids through a multidisciplinary approach.
The coordination environment around Cu(II) in highly concentrated solutions of copper(II) salts (CuCl(2) and Cu(Tf(2)N)(2)) in two pure ionic liquids bearing the same anion, namely, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf(2)N]) and 1-butyl-3-methylimidazolium chloride ([bmim]Cl), is investigated by X-ray photoelectron spectroscopy (XPS), UV/Vis spectroscopy, EPR spectroscopy and DFT calculations. Moreover, the electrochemical behavior of these mixtures is studied. Whereas reversible reduction of Cu(II) to copper metal can be observed in the 1:1 [bmim][Tf(2)N]:Cu(Tf(2)N)(2) solution, 2:1 and 1:1 [bmim]Cl:CuCl(2) mixtures showed one-electron reduction of Cu(II) to Cu(I) with formation of a permanent deposit of CuCl. XPS, UV/Vis and EPR spectra as well as DFT calculations suggest the formation in [bmim]Cl of dynamic coordination complexes arising from the interaction between CuCl(2) and [bmim](+)Cl(-). The two long-lived situations are probably trigonal and deformed tetrahedral copper(II) chloride coordination complexes ([CuCl(3)](-) and [CuCl(4)](2-), respectively).
Dipartimento di Chimica, Università di Firenze, via della Lastruccia 3, 50019 Sesto Fiorentino (FI), Italy.
Stefano
S
Caporali
Cinzia
C
Chiappe
Tiziana
T
Ghilardi
Christian Silvio
CS
Pomelli
Calogero
C
Pinzino