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 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 which 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.