Marta Falcone
The development of new processes for the selective and sustainable transformation of abundant small molecules constitutes one of the major research areas in inorganic and organometallic chemistry. These molecules as CO2, CO, N2 and H2 are abundant reservoirs of chemical energy, readily available sources of carbon, nitrogen and hydrogen. In a patent from 1909, Haber reported that uranium and uranium nitride were very efficient catalysts for ammonia synthesis. In order to perform multi-electron transfer, multimetallic complexes need to be designed. Reactivity of uranium bridging nitride remained unexplored since we investigated the nitride based reactivity of a dinuclear uranium(IV) bridging nitride complex towards small molecules such as CO2, yielding the first example of a uranium complex containing a bridging dicarbamate ligand, or CO, resulting in the complete cleavage in mild conditions of one of the strongest bonds in nature, or H2, yielding one of the few examples in f-elements of metal hydride, which is readily transferred to substrates such as CO2. Beyond the ligand based reactivity, we were interested in reducing the two metal centers to access a diuranium(III) bridging nitride, to pursue nitrogen activation. This complex was shown to have high flexibility, provided by the siloxide ligands, high reducing power and a bridging atom, the nitride, that holds together the uranium centers, with the possibility to bend upon nitrogen activation. This approach led us to the isolation of a hydrazido complex, resulting from the four-electron reduction of dinitrogen by the two metal centers. Moreover, complete cleavage of the NâN single bond was achieved by addition of CO to give two cyanate ligands or by addition of H2 to give ammonia. The nitride atom linker is nonetheless, too reactive to act as a spectator and it is involved in reactivity. Hence, we target the isolation of the analogue dinuclear U(III) complex with an oxide ligand as linker. This complex showed the same reactivity towards nitrogen but DFT revealed a more ionic character of the UâO bond nature with respect to the UâN bond, leading to different reactivity of the hydrazido fragment upon addition of CO and upon addition of H2, showing a smaller extent of activation in the oxo complex with respect to the nitride. The diuranium(III) bridging oxide complex showed interesting reactivity with H2, forming a bis-hydride complex capable of reducing CO2 beyond the formate level, to methanol.
EPFL2019
