Thorium(IV) and Uranium(IV) Thioether and Selenoether Complexes: Synthesis and An-ER2 (E = S, Se) Bonding Comparison.

Reactions of the rigid thioether- and selenoether-containing ligand salts [{Li(AE2Ph2)}2] (E = S or Se; AE2Ph2 = 4,5-bis(phenylchalcogenido)-2,7,9,9-tetramethylacridanide) with ThCl4(dme)2 or UCl4 (for E = Se) afforded the actinide chalcogenoether complexes [(AE2Ph2)2ThCl2] (E = S (1), Se (2)), and [(ASe2Ph2)2UCl2] (3). X-ray crystal structures of 1-3 revealed tetravalent actinide cations complexed to two κ3-coordinated AE2Ph2 ligands, with Th-ER2 and U-ER2 distances below the sum of the covalent radii. Complexes 1-3 provide extremely rare examples of thorium-thioether, thorium-selenoether, and uranium-selenoether bonds, and 1 and 2 contain the shortest known Th-SR2 and Th-SeR2 distances. DFT and QTAIM calculations confirm the presence of significant An(IV)-ER2 interactions in 1-3 and provide insight into the extent of covalency in the An-ER2 bonds.

Thorium(IV) and Uranium(IV) Thioether and Selenoether Complexes: Synthesis and An-ER2 (E = S, Se) Bonding Comparison. Journal Articles