Syntheses of N,N′-Bis(1-acetonylethylidene)ethylenediamine Complexes of Rare Earth Perchlorates

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N,N′-Bis(1-acetonylethylidene)ethylenediamine(AEH2) complexes were prepared by the reaction of hydrous rare earth perchlorates with AEH2 in methanol. Elemental analysis, X-ray powder diffraction analysis, pH titration, IR and luminescence spectrometries indicated that the complexes of the lighter rare earths were Ln(AEH2)4(ClO4)3, where Ln are La, Pr, Nd, and Sm, while the complexes of the heavier rare earths were hydroxocomplexes, Ln(AEH2)2(ClO4)2(OH)·H2O, where Ln are Gd, Dy, and Er. Anhydrous gadolinium perchlorate was reacted with AEH2 in methanol under anhydrous conditions to give Gd(AEH2)4(ClO4)3. It was possible that a water molecule played an important role in the complexation of rare earth perchlorates with AEH2 in methanol. The formation of the hydroxocomplexes with AEH2 was related to the low coordinating ability of the perchlorate ion and to the charge densities of the rare earth ions as well as to the basicity of AEH2.
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