Four-electron Reduction and Functionalization of N₂ by a Uranium(III) Bridging Nitride.

N2 is a cheap and widely available but very unreactive molecule. Notably, the only industrial process for the conversion of dinitrogen is the Haber-Bosch process to form ammonia, but under very harsh conditions (high temperature and pressure). Here, we review our recent research leading to the reduction of dinitrogen by four electrons, under ambient conditions by a uranium(III) bridging nitride, K3 U-N-U, where two uranium(III) cations are linked by a nitride group and a flexible metal-ligand scaffold. We also show that the bound dinitrogen can be further functionalized under mild conditions: the addition of acid, hydrogen and protons or carbon monoxide to the uranium hydrazido complex yields to the cleavage of the N-N single bond and to the formation of new N-H and N-C bonds.