Thorium(IV) and Uranium(IV) Thioether and Selenoether Complexes: Synthesis and An–ER<sub>2</sub> (E = S, Se) Bonding Comparison
Reactions of the rigid thioether- and selenoether-containing ligand salts [{Li(AE<sub>2</sub><sup>Ph2</sup>)}<sub>2</sub>] (E = S or Se; AE<sub>2</sub><sup>Ph2</sup> = 4,5-bis(phenylchalcogenido)-2,7,9,9-tetramethylacridanide) with ThCl<sub>4</sub>(dme)<sub>2</sub> or UCl<sub>4</sub> (for E = Se) afforded the actinide chalcogenoether complexes [(AE<sub>2</sub><sup>Ph2</sup>)<sub>2</sub>ThCl<sub>2</sub>] (E = S (<b>1</b>), Se (<b>2</b>)), and [(ASe<sub>2</sub><sup>Ph2</sup>)<sub>2</sub>UCl<sub>2</sub>] (<b>3</b>). X-ray crystal structures of <b>1</b>-<b>3</b> revealed tetravalent actinide cations complexed to two κ<sup>3</sup>-coordinated AE<sub>2</sub><sup>Ph2</sup> ligands, with Th-ER<sub>2</sub> and U-ER<sub>2</sub> distances below the sum of the covalent radii. Complexes <b>1</b>-<b>3</b> provide extremely rare examples of thorium-thioether, thorium-selenoether, and uranium-selenoether bonds, and <b>1</b> and <b>2</b> contain the shortest known Th-SR<sub>2</sub> and Th-SeR<sub>2</sub> distances. DFT and QTAIM calculations confirm the presence of significant An(IV)-ER<sub>2</sub> interactions in <b>1</b>-<b>3</b> and provide insight into the extent of covalency in the An-ER<sub>2</sub> bonds.
Authors
- Novan A. G. Gray (ORCID: https://orcid.org/0000-0003-3607-4063)
- David J. H. Emslie (ORCID: https://orcid.org/0000-0002-2570-9345)
Institutions
- McMaster University (CA)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2024-09-26
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c03074
- Citations
- 3
- Primary Topic
- Radioactive element chemistry and processing
- Type
- article
- Field-Weighted Citation Impact
- 0.48
Funders
- Government of Ontario
- Natural Sciences and Engineering Research Council of Canada