Ontology type: schema:ScholarlyArticle Open Access: True
2017-12-01
AUTHORSBenedict M. Gardner, Christos E. Kefalidis, Erli Lu, Dipti Patel, Eric J. L. McInnes, Floriana Tuna, Ashley J. Wooles, Laurent Maron, Stephen T. Liddle
ABSTRACTReversible 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. More... »
PAGES1898
http://scigraph.springernature.com/pub.10.1038/s41467-017-01363-0
DOIhttp://dx.doi.org/10.1038/s41467-017-01363-0
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