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

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...

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Bibliographic Details
Published in:Nature communications 2017-12, Vol.8 (1), p.1898-10, Article 1898
Main Authors: Gardner, Benedict M., Kefalidis, Christos E., Lu, Erli, Patel, Dipti, McInnes, Eric J. L., Tuna, Floriana, Wooles, Ashley J., Maron, Laurent, Liddle, Stephen T.
Format: Article
Language:English
Subjects:
639/638/263/406
639/638/77
639/638/911
Catalysis
Chemical reduction
Chemical Sciences
Electrons
Extrusion
Heavy metals
Humanities and Social Sciences
Labeling
Metals
multidisciplinary
Organic compounds
Oxidation
Physics
Science
Science (multidisciplinary)
Transition metals
Uranium
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Summary: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. The reactivity of f-block complexes is primarily defined by single-electron oxidations and σ-bond metathesis. Here, Liddle and co-workers provide evidence that a uranium complex can undergo reversible oxidative addition and reductive elimination, demonstrating transition metal-like reactivity within f-block chemistry.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-017-01363-0