Evidence for ligand- and solvent-induced disproportionation of uranium(IV)
AuthorsDu, Jingzhen; orcid: 0000-0003-4037-9281
Douair, Iskander; orcid: 0000-0002-7482-5510
Lu, Erli; orcid: 0000-0002-0619-5967
Seed, John A.; orcid: 0000-0002-3751-0325
Tuna, Floriana; orcid: 0000-0002-5541-1750
Wooles, Ashley J.
Maron, Laurent; orcid: 0000-0003-2653-8557; email: firstname.lastname@example.org
Liddle, Stephen T.; orcid: 0000-0001-9911-8778; email: email@example.com
MetadataShow full item record
AbstractAbstract: 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.
CitationNature Communications, volume 12, issue 1, page 4832
PublisherNature Publishing Group UK
DescriptionFrom Springer Nature via Jisc Publications Router
History: received 2020-05-14, accepted 2021-07-21, registration 2021-07-28, pub-electronic 2021-08-10, online 2021-08-10, collection 2021-12
Publication status: Published
Funder: RCUK | Engineering and Physical Sciences Research Council (EPSRC); doi: https://doi.org/10.13039/501100000266; Grant(s): EP/K024000/1, EP/M027015/1, EP/P001386/1, EP/S033181/1
Funder: Leverhulme Trust; doi: https://doi.org/10.13039/501100000275; Grant(s): RF-2018-545\4
Funder: Royal Society; doi: https://doi.org/10.13039/501100000288; Grant(s): UF110005
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