Search

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. [ABSTRACT FROM AUTHOR]

Keywords: bonding; covalency; selenoether; thioether; uranium EN bonding covalency selenoether thioether uranium 1 1 1 01/06/22 20220103 NES 220103 B Uranium - selenoether linkages b have been accessed for the first time, enabling the study of U-SeR SB 2 sb versus U-SR SB 2 sb and U-OR SB 2 sb bonding. Bonding, covalency, selenoether, thioether, uranium The shape of the uranium selenoether complex resembles a butterfly, and the cover art depicts a metamorphosis from the protio-ligand (caterpillar), to the potassium salt of the ligand (chrysalis), to the uranium complex (butterfly). [Extracted from the article]

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. [ABSTRACT FROM AUTHOR]