Comparisons of lanthanide/actinide+2 ions in a tris(aryloxide)arene coordination environment

A new series of Ln(3+) and Ln(2+) complexes has been synthesized using the tris(aryloxide) arene ligand system, (((ArO)-Ar-Ad,Me)(3)mes)(3-), recently used to isolate a complex of U2+. The triphenol precursor, ((ArOH)-Ar-Ad,Me)(3)mes, reacts with the Ln(3+) amides, Ln(NR2)(3) (R = SiMe3), to form a series of [(((ArO)-Ar-Ad,Me)(3)mes)Ln] complexes, 1-Ln. Crystallographic characterization was achieved for Ln = Nd, Gd, Dy, and Er. The complexes 1-Ln can be reduced with potassium graphite in the presence of 2.2.2-cryptand (crypt) to form highly absorbing solutions with properties consistent with Ln(2+) complexes, [K(crypt)][(((ArO)-Ar-Ad,Me)(3)mes)Ln], 2-Ln. The synthesis of the Nd2+ complex [K(crypt)][(((ArO)-Ar-Ad,Me)(3)mes)Nd], 2-Nd, was unambiguously confirmed by X-ray crystallography. In the case of the other lanthanides, crystals were found to contain mixtures of 2-Ln co-crystallized with either a Ln(3+) hydride complex, [K(crypt)][(((ArO)-Ar-Ad,Me)(3)mes)LnH], 3-Ln, for Ln = Gd, Dy, and Er, or a hydroxide complex, [K(crypt)][(((ArO)-Ar-Ad,Me)(3)mes)Ln(OH)], 4-Ln, for Ln = Dy. A Dy2+ complex with 18-crown-6 as the potassium chelator, [K(18-crown-6)(THF)(2)][(((ArO)-Ar-Ad, Me)(3)mes) Dy], 5-Dy, was isolated as a co-crystallized mixture with the Dy3+ hydride complex, [K(18-crown-6)(THF)(2)][(((ArO)-Ar-Ad, Me)(3)mes)DyH], 6-Dy. Structural comparisons of 1-Ln and 2-Ln are presented with respect to their uranium analogs and correlated with density functional theory calculations on their electronic structures.