Uranium Going the Soft Way: Low-Valent Uranium(III) Coordinated to an Arene-Anchored Tris-Thiophenolate Ligand

Pividori DM, Miehlich M, Kestel B, Heinemann FW, Scheurer A, Patzschke M, Meyer K (2021)

Publication Type: Journal article

Publication year: 2021

Journal

Inorganic Chemistry American Chemical Society

Book Volume: 60

Pages Range: 16455-16465

Journal Issue: 21

DOI: 10.1021/acs.inorgchem.1c02310

Abstract

The synthesis of a tripodal, S-based ligand, namely the mesitylene-anchored, tris-thiophenolate-functionalized (mes(Me,AdArS)3)3- (1)3-, and its coordination chemistry with low-valent uranium to form [UIII((SArAd,Me)3mes)] (1-U) are reported. Single-crystal X-ray diffraction analysis reveals a C3-symmetric molecular structure. Full characterization of 1-U was performed using nuclear magnetic resonance, UV-vis-NIR electronic absorption, and electron paramagnetic resonance spectroscopies as well as SQUID magnetometry, thus confirming the U(III) oxidation state. Alternating current magnetic studies show that 1-U exhibits single-molecule magnet behavior at low temperatures in a non-zero external field. Comparison of these results to those of the previously reported mesitylene-anchored complexes, [UIII((OArAd,Me)3mes)] and [UIII((OArtBu,tBu)3mes)], indicates a drastic change in the electronic structure when moving from phenolate-based ligands to thiophenolate-based 1, which is further discussed by means of computational analysis (NBO, DFT, and QTAIM). Despite the U-O bonds being stronger, a much higher covalency was found for the U-S analogue.

Authors with CRIS profile

Daniel Maximilian Pividori Lehrstuhl für Anorganische und Allgemeine Chemie Matthias Miehlich Lehrstuhl für Anorganische und Allgemeine Chemie Benedikt Kestel Lehrstuhl für Anorganische und Allgemeine Chemie Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie Andreas Scheurer Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Helmholtz-Zentrum Dresden-Rossendorf (HZDR) DE Germany (DE)

How to cite

APA:

Pividori, D.M., Miehlich, M., Kestel, B., Heinemann, F.W., Scheurer, A., Patzschke, M., & Meyer, K. (2021). Uranium Going the Soft Way: Low-Valent Uranium(III) Coordinated to an Arene-Anchored Tris-Thiophenolate Ligand. Inorganic Chemistry, 60(21), 16455-16465. https://dx.doi.org/10.1021/acs.inorgchem.1c02310

MLA:

Pividori, Daniel Maximilian, et al. "Uranium Going the Soft Way: Low-Valent Uranium(III) Coordinated to an Arene-Anchored Tris-Thiophenolate Ligand." Inorganic Chemistry 60.21 (2021): 16455-16465.

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