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

Fieser ME, Palumbo CT, la Pierre HS, Halter D, Voora VK, Ziller JW, Furche F, Meyer K, Evans WJ (2017)

Publication Type: Journal article

Publication year: 2017

Journal

Chemical Science Royal Society of Chemistry

Book Volume: 8

Pages Range: 7424-7433

Journal Issue: 11

DOI: 10.1039/c7sc02337e

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.

Authors with CRIS profile

Henry Storms la Pierre Lehrstuhl für Anorganische und Allgemeine Chemie Dominik Halter Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

University of California Irvine

United States (USA) (US)

How to cite

APA:

Fieser, M.E., Palumbo, C.T., la Pierre, H.S., Halter, D., Voora, V.K., Ziller, J.W.,... 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

MLA:

Fieser, Megan E., et al. "Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment." Chemical Science 8.11 (2017): 7424-7433.

BibTeX: Download