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Evidence for single metal two electron oxidative addition and reductive elimination at uranium

Lookup NU author(s): Dr Erli Lu

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Abstract

© 2017 The Author(s). Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one-or multi-electron oxidation or reduction reactions. Here we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction that satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests that nitrenes are not generated and thus a reductive elimination has occurred. Though not optimally balanced in this case, this work presents evidence that classical d-block redox chemistry can be performed reversibly by f-block metals, and that uranium can thus mimic elementary transition metal reactivity, which may lead to the discovery of new f-block catalysis.

Publication metadata

Author(s): Gardner BM, Kefalidis CE, Lu E, Patel D, McInnes EJL, Tuna F, Wooles AJ, Maron L, Liddle ST

Publication type: Article

Publication status: Published

Journal: Nature Communications

Year: 2017

Volume: 8

Issue: 1

Online publication date: 01/12/2017

Acceptance date: 02/04/2016

Date deposited: 02/10/2019

ISSN (print): 2041-1723

Publisher: Nature Publishing Group

URL: https://doi.org/10.1038/s41467-017-01363-0

DOI: 10.1038/s41467-017-01363-0

PubMed id: 29196691

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