Uranium(IV) Thio‐ and Selenoether Complexes: Syntheses, Structures, and Computational Investigation of U−ER 2 Interactions Academic Article uri icon

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abstract

  • Rigid thioether- and selenoether-containing pincer proligands H[AS2 Ph2 ] (1) and H[ASe2 Ph2 ] (2) were synthesized, and deprotonation provided the potassium salts [K(AS2 Ph2 )(dme)] (3) and [K(ASe2 Ph2 )(dme)2 ] (4). Reaction of two equivalents of 3 or 4 with [UI4 (dioxane)2 ] afforded the uranium thioether complex [(AS2 Ph2 )2 UI2 ] (5) and the first example of a uranium-selenoether complex, [(ASe2 Ph2 )2 UI2 ] (6). X-ray structures revealed distorted square antiprismatic geometries in which the AE2 Ph2 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.

publication date

  • January 3, 2022