Evidence for ligand- and solvent-induced disproportionation of uranium(IV)

Jingzhen Du, Iskander Douair, Erli Lu, John A. Seed, Floriana Tuna, Ashley J. Wooles, Laurent Maron () and Stephen T. Liddle ()
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Jingzhen Du: The University of Manchester
Iskander Douair: Université Paul Sabatier
Erli Lu: The University of Manchester
John A. Seed: The University of Manchester
Floriana Tuna: The University of Manchester
Ashley J. Wooles: The University of Manchester
Laurent Maron: Université Paul Sabatier
Stephen T. Liddle: The University of Manchester

Nature Communications, 2021, vol. 12, issue 1, 1-12

Abstract: Abstract Disproportionation, where a chemical element converts its oxidation state to two different ones, one higher and one lower, underpins the fundamental chemistry of metal ions. The overwhelming majority of uranium disproportionations involve uranium(III) and (V), with a singular example of uranium(IV) to uranium(V/III) disproportionation known, involving a nitride to imido/triflate transformation. Here, we report a conceptually opposite disproportionation of uranium(IV)-imido complexes to uranium(V)-nitride/uranium(III)-amide mixtures. This is facilitated by benzene, but not toluene, since benzene engages in a redox reaction with the uranium(III)-amide product to give uranium(IV)-amide and reduced arene. These disproportionations occur with potassium, rubidium, and cesium counter cations, but not lithium or sodium, reflecting the stability of the corresponding alkali metal-arene by-products. This reveals an exceptional level of ligand- and solvent-control over a key thermodynamic property of uranium, and is complementary to isolobal uranium(V)-oxo disproportionations, suggesting a potentially wider prevalence possibly with broad implications for the chemistry of uranium.

Date: 2021
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DOI: 10.1038/s41467-021-25151-z

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