Pushing the boundary of covalency in lanthanoid-tellurium bonds: Insights from synthesis, molecular and electronic structures of low-coordinate, monomeric europium(II) and ytterbium(II) tellurolates.

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 the secondary bonding interaction stabilized hybrid organotellurolate ligands. The reaction of bis[2-((dimethylamino)methyl)phenyl] ditelluride, 1 and 8,8'-diquinolinyl ditelluride, 2 with Ln0 metal (Ln = Eu, Yb) resulted in the formation of monomeric complexes [LnII(TeR)2(Solv)2] [R = C6H4(CH2NMe2)-2] [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.