Uranium(IV) Thio‐ and Selenoether Complexes: Syntheses, Structures, and Computational Investigation of U−ER<sub>2</sub>Interactions

AbstractRigid thioether‐ and selenoether‐containing pincer proligands H[AS2] (1) and H[ASe2] (2) were synthesized, and deprotonation provided the potassium salts [K(AS2)(dme)] (3) and [K(ASe2)(dme)2] (4). Reaction of two equivalents of3or4with [UI4(dioxane)2] afforded the uranium thioether complex [(AS2)2UI2] (5) and the first example of a uranium‐selenoether complex, [(ASe2)2UI2] (6). X‐ray structures revealed distorted square antiprismatic geometries in which the AE2ligands are κ3‐coordinated. The nature of the U−ER2bonding in5and6, as well as methyl‐free analogues of5and6and a hypothetical ether analogue, was investigated computationally (including NBO, AIM, and ELF calculations) illustrating increasing covalency from O to S to Se.

Uranium(IV) Thio‐ and Selenoether Complexes: Syntheses, Structures, and Computational Investigation of U−ER₂Interactions Journal Articles