Metal versus Ligand Reduction in Ln3+ Complexes of a Mesitylene-Anchored Tris(Aryloxide) Ligand

Palumbo CT, Halter D, Voora VK, Chen GP, Chan AK, Fieser ME, Ziller JW, Hieringer W, Furche F, Meyer K, Evans WJ (2018)

Publication Type: Journal article

Publication year: 2018

Journal

Inorganic Chemistry American Chemical Society

Book Volume: 57

Pages Range: 2823-2833

Journal Issue: 5

DOI: 10.1021/acs.inorgchem.7b03236

Abstract

The synthesis of 4fn Ln3+ complexes of the tris(aryloxide) mesitylene ligand, ((Ad,MeArO)3mes)3-, with Ln = La, Ce, Pr, Sm, and Yb, and their reduction with potassium have revealed that this ligand system can be redox active with some metals. Protonolysis of [Ln(N(SiMe3)2)3] (Ln = La, Ce, Pr, Sm, Yb) with the tris(phenol) (Ad,MeArOH)3mes yielded the Ln3+ complexes [((Ad,MeArO)3mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 1-Ln. Single electron reduction of each 4fn complex, 1-Ln, using potassium yielded the reduced products, [K(2.2.2-cryptand)][((Ad,MeArO)3mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 2-Ln. The Sm and Yb complexes have properties consistent with the presence of Ln2+ ions with traditional 4fn+1 electron configurations. However, the La, Ce, and Pr complexes appear to formally contain Ln3+ ions and ((Ad,MeArO)3mes)4- ligands. Structural comparisons of the [((Ad,MeArO)3mes)Ln] and [((Ad,MeOAr)3mes)Ln]1- complexes along with UV-vis absorption and EPR spectroscopy as well as density functional theory calculations support these ground state assignments.

Authors with CRIS profile

Dominik Halter Lehrstuhl für Anorganische und Allgemeine Chemie Wolfgang Hieringer Lehrstuhl für Theoretische Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

University of California Irvine US United States (USA) (US)

How to cite

APA:

Palumbo, C.T., Halter, D., Voora, V.K., Chen, G.P., Chan, A.K., Fieser, M.E.,... Evans, W.J. (2018). Metal versus Ligand Reduction in Ln3+ Complexes of a Mesitylene-Anchored Tris(Aryloxide) Ligand. Inorganic Chemistry, 57(5), 2823-2833. https://dx.doi.org/10.1021/acs.inorgchem.7b03236

MLA:

Palumbo, Chad T., et al. "Metal versus Ligand Reduction in Ln3+ Complexes of a Mesitylene-Anchored Tris(Aryloxide) Ligand." Inorganic Chemistry 57.5 (2018): 2823-2833.

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