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

Megan E. Fieser, Chad T. Palumbo, Henry S. La Pierre, Dominik P. Halter, Vamsee K. Voora, Joseph W. Ziller, Filipp Furche, Karsten Meyer, William J. Evans

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30 Scopus citations

Abstract

A new series of Ln3+ and Ln2+ complexes has been synthesized using the tris(aryloxide)arene ligand system, ((Ad,MeArO)3mes)3-, recently used to isolate a complex of U2+. The triphenol precursor, (Ad,MeArOH)3mes, reacts with the Ln3+ amides, Ln(NR2)3 (R = SiMe3), to form a series of [((Ad,MeArO)3mes)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 Ln2+ complexes, [K(crypt)][((Ad,MeArO)3mes)Ln], 2-Ln. The synthesis of the Nd2+ complex [K(crypt)][((Ad,MeArO)3mes)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 Ln3+ hydride complex, [K(crypt)][((Ad,MeArO)3mes)LnH], 3-Ln, for Ln = Gd, Dy, and Er, or a hydroxide complex, [K(crypt)][((Ad,MeArO)3mes)Ln(OH)], 4-Ln, for Ln = Dy. A Dy2+ complex with 18-crown-6 as the potassium chelator, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)Dy], 5-Dy, was isolated as a co-crystallized mixture with the Dy3+ hydride complex, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)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.

Original languageEnglish (US)
Pages (from-to)7424-7433
Number of pages10
JournalChemical Science
Volume8
Issue number11
DOIs
StatePublished - 2017

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    Fieser, M. E., Palumbo, C. T., La Pierre, H. S., Halter, D. P., Voora, V. K., Ziller, J. W., Furche, F., Meyer, K., & Evans, W. J. (2017). Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment. Chemical Science, 8(11), 7424-7433. https://doi.org/10.1039/c7sc02337e