Tetranuclear Hydroxo Complexes of Rare-Earth Elements with the Cubane Core as Products of Self-Controlled Hydrolysis

Abstract

Tetranuclear hydroxo complexes [La4(Deta)4(OH)4(Tfa)3(DetadcH)2](HTfa)(H2O)7(Tfa)3 (I) and [Nd4(Deta)4(OH)4(Tfa)3(DetadcH)2](H2O)n(Tfa)3 (II) with diethylene-N,N′-dicarbamate anions (DetadcH–) are synthesized for the first time by the reactions of lanthanum trifluoroacetate and neodymium trifluoroacetate with a solution of diethylenetriamine (Deta) in air under the self-controlled hydrolysis conditions and are characterized by X-ray diffraction, powder X-ray diffraction, IR spectroscopy, and elemental analysis. Compounds I and II contain the same-type complex cationic fragment with the cubane metal–oxygen core stabilized due to four chelate Deta ligands and two bridging DetadcH– ligands. The DFT calculations of the geometry and vibrational spectrum of the [La4(Deta)4(OH)4(Tfa)3(DetadcH)2]3+ complex cation are performed.