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Updated: Oct 11, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Uranium(IV) Thio- and Selenoether Complexes: Syntheses, Structures, and Computational Investigation of U-ER2
Novan A G Gray1, Jeffrey S Price1, David J H Emslie1
1Department of Chemistry and Chemical Biology, McMaster University, 1280 Main Street West, Hamilton, Ontario, L8S 4M1, Canada.
Abstract:
Rigid 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 of 3 or 4 with [UI4 (dioxane)2 ] afforded the uranium thioether complex [(AS2 )2 UI2 ] (5) and the first example of a uranium-selenoether complex, [(ASe2 )2 UI2 ] (6). X-ray structures revealed distorted square antiprismatic geometries in which the AE2 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.
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