Uranium(IV) Thio‐ and Selenoether Complexes: Syntheses, Structures, and Computational Investigation of U−ER₂ Interactions.

Gray, Novan A. G.; Price, Jeffrey S.; Emslie, David J. H.

Rigid thioether‐ and selenoether‐containing pincer proligands H[AS2Ph2 ] (1) and H[ASe2Ph2 ] (2) were synthesized, and deprotonation provided the potassium salts [K(AS2Ph2)(dme)] (3) and [K(ASe2Ph2)(dme)2] (4). Reaction of two equivalents of 3 or 4 with [UI4(dioxane)2] afforded the uranium thioether complex [(AS2Ph2)2UI2] (5) and the first example of a uranium‐selenoether complex, [(ASe2Ph2)2UI2] (6). X‐ray structures revealed distorted square antiprismatic geometries in which the AE2Ph2 ligands are κ3‐coordinated. The nature of the U−ER2 bonding in 5 and 6, as well as methyl‐free analogues of 5 and 6 and a hypothetical ether analogue, was investigated computationally (including NBO, AIM, and ELF calculations) illustrating increasing covalency from O to S to Se.

URANIUM; POTASSIUM salts; DIOXANE; PROTON transfer reactions; SELENOPROTEINS; CHALCOGENS

Chemistry - A European Journal, 2022, Vol 28, Issue 1, p1

0947-6539

Academic Journal

10.1002/chem.202103580