Why Is Fecl3 The Product, When Fe And Cl2 Reacts And Not Fecl2?

Publication History Received14 September 2000Published online3 April 2001Published inissue 1 May 2001

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We have prepared ionic liquids by mixing either iron(II) chloride or iron(III) chloride with 1-butyl-3-methylimidazolium chloride (BMIC). Iron(II) chloride forms ionic liquids from a mole ratio of 1 FeCl2/3 BMIC to almost 1 FeCl2/1 BMIC. Both Raman scattering and ab initio calculations indicate that FeCl42- is the predominant iron-containing species in these liquids. Iron(III) chloride forms ionic liquids from a mole ratio of 1 FeCl3/1.9 BMIC to 1.7 FeCl3/1 BMIC. When BMIC is in excess, Raman scattering indicates the presence of FeCl4-. When FeCl3 is in excess, Fe2Cl7- begins to appear and the amount of Fe2Cl7- increases with increasing amounts of FeCl3. Ionic liquids were also prepared from a mixture of FeCl2 and FeCl3 and are discussed. Finally, we have used both Hartree−Fock and density functional theory methods to compute the optimized structures and vibrational spectra for these species. An analysis of the results using an all-electron basis set, 6-31G*, as well as two different effective core potential basis sets, LANL2DZ and CEP-31G is presented.

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Corresponding author: Griff Freeman, SurroMed, Inc., 2375 Garcia Ave., Mountain View, CA 94043. E-mail:

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Cartesian coordinates for all Fe(III) and Fe(II) structures determined by computation. Raman spectra for FeCl3/BMIC at 1.7/1, 1.5/1, 1/1, 1/1.1, 1/1.3, 1/1.5, and 1/1.7 ratios. Raman spectra for FeCl2/BMIC at 1/2 and 1/3 ratios. This material is available free of charge via the Internet at https://lize.vn.

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