Synthesis and characterization of isopropylamine complexes of lanthanide(II) diiodides: Molecular structure of TmI2(PriNH2)4 and EuI2(PriNH2)4

It was found that the lanthanide diiodides LnI2 (1) (Ln = Nd, Sm, Eu, Dy, Tm, Yb) are dissolved in isopropylamine (IPA) without redox transformations. Stability of the formed solutions decreases in a row Eu ≈ Yb > Sm > Tm > Dy > Nd. Removing of a solvent in vacuum leaves complexes LnI2(IPA)x (2) (Nd, x = 5; Sm, Eu, Dy, Tm, Yb, x = 4) as crystalline colored solids. Stability of 2-Nd,Dy,Tm is higher than that of known THF or DME coordinated salts. Divalent state of metal in the products is confirmed by data of UV–Vis spectroscopy, magnetic measurements and their chemical behavior. Structure of 2-Eu and 2-Tm was established by X-ray diffraction analysis. Oxidation of 2-Nd,Dy in IPA affords amine-amides (PriNH)Ln(IPA)y (3) (Nd, y = 4; Dy, x = 3). n-Propylamine also dissolves the iodides 1-Sm,Eu,Dy,Tm,Yb but stability of the solutions is significantly lower. 1-Nd vigorously reacts with PrnNH2 even at −30 °C which hampers the formation of the solution.

The diiodides LnI2 (Ln = Nd, Sm, Eu, Dy, Tm, Yb) dissolve in isopropylamine (IPA) to give colored solutions removing the solvent from which leaves the divalent complexes LnI2(IPA)x (x = 4, 5). Structure of Tm and Eu derivatives was established by X-ray diffraction. Redox transformations of LnI2 in the solutions lead to formation of trivalent amides (PriNH)Ln(IPA)y.Figure optionsDownload as PowerPoint slide