Electrochemical and Spectroscopic Investigation of Ln3+ (Ln = Sm, Eu, and Yb) Solvation in Bis(trifluoromethylsulfonyl)imide-Based Ionic Liquids and Coordination by N,N,N′,N′-Tetraoctyl-3-oxa-pentane Diamide (TODGA) and Chloride

Abstract

The electrochemistry and electronic absorption spectroscopy of samarium, europium, and ytterbium were investigated in the 1-(1-butyl)trimethylammonium bis(trifluoromethylsulfonyl)imide (BuMe3NTf2N) and 1-butyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BuMePyroTf2N) ionic liquids and in these solvents containing the neutral tridentate ligand N,N,N',N'-tetraoctyl-3-oxo-pentane diamide (TODGA) and the anionic hard ligand chloride. Lanthanide ions were introduced into the ionic liquids by controlled potential oxidation of the respective metals to yield solutions containing Eu(2+), Sm(3+), and Yb(3+), and it was possible to cycle between Eu(2+) and Eu(3+) as well as Yb(3+) and Yb(2+) using controlled potential electrolysis. Electronic absorption spectroscopy suggested that the Ln(3+) species are weakly solvated by Tf2N(-) anions as [Ln(Tf2N)x]((x-3)-) in the neat ILs. The quasireversible Ln(3+/2+) couples of all three elements were readily accessible in these ILs, but Sm(2+) was only stable on the voltammetric time scale. Addition of TODGA to [Ln(Tf2N)x]((x-3)-) solutions produces 3:1 complexes with Eu(3+) and Sm(3+) but only a 2:1 complex with the smaller Yb(3+) ion. Depending on the temperature, addition of Cl(-) to solutions of [Ln(Tf2N)x]((x-3)-) induces precipitation of LnCl3(s) when the mole ratio mCl(-)/mLn(3+) ≈ 3. However, when mCl(-)/mLn(3+) > 3, these precipitates redissolve to form the octahedral chloride complexes, [LnCl6](3-).