Evidence for ligand- and solvent-induced disproportionation of uranium(IV) - Archive ouverte HAL
Article Dans Une Revue Nature Communications Année : 2021

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

Résumé

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. Disproportion of uranium(IV) is rare, as it is usually the stable product of uranium(III) or (V) disproportionation. Here, the authors report uranium(IV) disproportionation to uranium(III) and (V) revealing ligand and solvent control over a key thermodynamic property of uranium
Fichier principal
Vignette du fichier
s41467-021-25151-z.pdf (2.56 Mo) Télécharger le fichier
Origine Fichiers éditeurs autorisés sur une archive ouverte

Dates et versions

hal-03717266 , version 1 (08-07-2022)

Licence

Identifiants

Citer

Jingzhen Du, Iskander Douair, Erli Lu, John A. Seed, Floriana Tuna, et al.. Evidence for ligand- and solvent-induced disproportionation of uranium(IV). Nature Communications, 2021, 12, pp.4832. ⟨10.1038/s41467-021-25151-z⟩. ⟨hal-03717266⟩
23 Consultations
31 Téléchargements

Altmetric

Partager

More