Inorganic & Coordination Chemistry, Short talk
IC-027

Small Molecule Activation at Multimetallic Uranium Nitrides

M. Falcone1
1EPF Lausanne

Uranium nitrides are attractive candidates for stoichiometric and catalytic N-transfer reactions, small molecule transformation, [1] and for advanced nuclear fuels. The N-C bond formation reactions are key steps in the construction of value-added chemical compounds. Recently we reported remarkable reactivity studies in f-element chemistry. Particularly desirable are the synthetic methods using cheap and available C1 feedstock such as carbon dioxide or carbon monoxide.[2] Tert-butoxysiloxides were shown to be very effective ligands in supporting the reactivity of low valent f elements with small molecules.[3],[4] In particular, it was recently reported the remarkable reactivity of the previously described nitride bridged diuranium(IV) complex [Cs{[U(OSi(OtBu)3)3]2(μ-N)}] with CO2, CS2, and CO, yielding to diverse N-functionalized products 5,6. Moreover, very recent results show that increasing the electron density by reducing the metal centers leads to a multimetallic K3UNU nitride bridged diuranium(III) complex, 1 (Figure 1) which shows extraordinary reactivity towards the dinitrogen molecule. We will present the reduction and further functionalization of dinitrogen in ambient condition by a uranium nitride 7.

[1]  a) F. Haber, German patent, 1909, vol. DE229126; b) A. R. Fox, S. C. Bart, K. Meyer, C. C. Cummins, Nature, 2008, 455, 341
[2] M. Aresta, A. Dibenedetto, J. Chem. Soc.-Dalton trans., 2007, 2975
[3] J. Andrez, M. Mazzanti, Angew. Chem., 2014, 126, 10616
[4] O. Cooper, M. Mazzanti, J. Am. Chem. Soc., 2014, 136, 6716
[5]  M. Falcone, L. Chatelain, M. Mazzanti, Angew. Chem. Int. Ed., 2016, 55, 4074
[6]  M. Falcone, L. Maron, M. Mazzanti, , Angew. Chem. Int. Ed., 2016, 55, 12290
[7]  M. Falcone, L. Chatelain, M. Mazzanti, manuscript submitted