Synthesis, structure and redox properties of single-atom bridged diuranium complexes supported by aryloxides.

Dalton Trans

Group of Coordination Chemistry, Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), 1015, Lausanne, Switzerland.

Published: August 2024


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Article Abstract

Single-atom (group 15 and group 16 anions) bridged dimetallic complexes of low oxidation state uranium provide a convenient route to implement multielectron transfer and promote magnetic communication in uranium chemistry, but remain extremely rare. Here we report the synthesis, redox and magnetic properties of N, O, and S bridged diuranium complexes supported by bulky aryloxide ligands. The U(IV)/U(IV) nitride [Cs(THF)][(U(OAr))(μ-N)], 1 could be prepared and characterized but could not be reduced. Reduction of the neutral U(IV)/U(IV) complexes [(U(OAr))(μ-X)] A (X = O) and B (X = S) led to the isolation and characterization of the U(IV)/U(III) and U(III)/U(III) analogues. Complexes [(K(THF))(U(OAr))(μ-S)], 5 and [K(2.2.2-cryptand)][(U(OAr))(μ-S)], 6 are the first examples of U(III) sulphide bridged complexes. Computational studies and redox properties allow the reactivity of the dimetallic complexes to be related to their electronic structure.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11320667PMC
http://dx.doi.org/10.1039/d4dt01819bDOI Listing

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