It is known that nano- or microcrystalline aluminium may be electrodeposited from mixtures of AlCl(3) and the ionic liquids 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([BMP]Tf(2)N) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMIm]Tf(2)N), and that two phases form with higher formal concentrations of AlCl(3) (at 1.6 mol L(-1) (x(Al)=0.33) and 2.5 mol L(-1) (x(Al)=0.39), respectively). This account analyzes the hitherto unknown molecular nature of these mixtures by a detailed experimental (multinuclear NMR and Raman spectroscopies) and theoretical study (BP86/TZVP DFT calculations, including COSMO solvation energies). The addition of AlCl(3) to the two liquids first leads to complexation with [Tf(2)N](-) and then disproportionation of the initial [AlCl(x)(Tf(2)N)(y)](-) complexes give Al(Tf(2)N)(3) and [AlCl(4)](-). At high concentrations of AlCl(3), the lower phase consists almost completely of Al(Tf(2)N)(3), whereas in the upper phase [AlCl(4)](-) is the dominant species. Electrodeposition of aluminium in the upper phase occurs from mixed AlCl(x)(Tf(2)N)(y) species, most likely from [AlCl(2)(Tf(2)N)(2)](-) formed in small concentrations at the phase boundary between the [AlCl(4)](-) and the Al(Tf(2)N)(3) layers. All the findings are supported by DFT calculations as well as an X-ray crystal structure determination of Al(Tf(2)N)(3). The latter was separated from the mixture by sublimation on a preparative scale. It was independently prepared from AlEt(3) and HNTf(2) and fully characterized. Moreover, the ionic liquids [BMP]AlCl(4) (m.p. 74 degrees C) and [EMIm]AlCl(4) (m.p. -7 degrees C), which mainly form the upper layer in the biphasic regime, were independently prepared and also fully characterized.

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