Pushing the Boundary of Covalency in Lanthanoid-Tellurium Bonds: Insights from the Synthesis, Molecular and Electronic Structures of Low-Coordinate, Monomeric Europium(II) and Ytterbium(II) Tellurolates

Deka, Rajesh, Dey, Sourav, Guo, Zhifang, Butcher, Ray J., Junk, Peter C., Turner, David R., Singh, Harkesh B., and Deacon, Glen B. (2023) Pushing the Boundary of Covalency in Lanthanoid-Tellurium Bonds: Insights from the Synthesis, Molecular and Electronic Structures of Low-Coordinate, Monomeric Europium(II) and Ytterbium(II) Tellurolates. Chemistry - A European Journal, 29. e202301054.

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Abstract

Owing to the strict hard/soft dichotomy between the lanthanoids and tellurium atoms, and the strong affinity of lanthanoid ions for high coordination numbers, low-coordinate, monomeric lanthanoid tellurolate complexes have remained elusive as compared to the lanthanoid complexes with lighter group 16 elements (O, S, and Se). This makes the development of suitable ligand systems for low-coordinate, monomeric lanthanoid tellurolate complexes an appealing endeavor. In a first report, a series of low-coordinate, monomeric lanthanoid (Yb, Eu) tellurolate complexes were synthesized by utilizing hybrid organotellurolate ligands containing N-donor pendant arms. The reaction of bis[2-((dimethylamino)methyl)phenyl] ditelluride, 1 and 8,8′diquinolinyl ditelluride, 2 with Ln0 metals (Ln=Eu, Yb) resulted in the formation of monomeric complexes [LnII(TeR)2(Solv)2] [R=C6H4-2-CH2NMe2] [3: Ln=Eu, Solv=tetrahydrofuran; 4: Ln=Eu, Solv=acetonitrile; 5: Ln=Yb, Solv=tetrahydrofuran; 6: Ln=Yb, Solv=pyridine] and [EuII(TeNC9H6)2(Solv)n] (7: Solv=tetrahydrofuran, n=3; 8: Solv=1,2-dimethoxyethane, n=2), respectively. Complexes 3–4 and 7–8 represent the first sets of examples of monomeric europium tellurolate complexes. The molecular structures of complexes 3–8 are validated by single–crystal X-ray diffraction studies. The electronic structures of these complexes were investigated using Density Functional Theory (DFT) calculations, which revealed appreciable covalency between the tellurolate ligands and lanthanoids.

Item ID: 79206
Item Type: Article (Research - C1)
ISSN: 1521-3765
Keywords: europium, lanthanoid, low-coordinate, monomer, tellurium
Copyright Information: © 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.
Funders: Australian Research Council (ARC)
Projects and Grants: ARC DP190100798, ARC DP230100112
Date Deposited: 26 Sep 2023 00:52
FoR Codes: 34 CHEMICAL SCIENCES > 3402 Inorganic chemistry > 340203 F-block chemistry @ 100%
SEO Codes: 28 EXPANDING KNOWLEDGE > 2801 Expanding knowledge > 280105 Expanding knowledge in the chemical sciences @ 100%
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