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

Benedict M. Gardner, Christos E. Kefalidis, Erli Lu, Dipti Patel, Eric J. L. McInnes, Floriana Tuna, Ashley J. Wooles, Laurent Maron () and Stephen T. Liddle ()
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Benedict M. Gardner: The University of Manchester
Christos E. Kefalidis: Université Paul Sabatier
Erli Lu: The University of Manchester
Dipti Patel: University of Nottingham
Eric J. L. McInnes: 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, 2017, vol. 8, issue 1, 1-10

Abstract: Abstract 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.

Date: 2017
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DOI: 10.1038/s41467-017-01363-0

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