Lookup NU author(s): Dr Erli Lu
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
© 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.
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
Online publication date: 01/12/2017
Acceptance date: 02/04/2016
Date deposited: 02/10/2019
ISSN (print): 2041-1723
Publisher: Nature Publishing Group
PubMed id: 29196691
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