N2is a cheap and widely available but very unreactive molecule.[1]Notably the only industrial process so far using dinitrogen is the Haber-Bosch that produces ammonia, but uses very harsh conditions. Before iron-based catalysts were used in the Haber Bosch process, uranium metal and uranium(III) nitride materials were shown to be very effective catalysts for the production of ammonia from dinitrogen. However, only a few examples of uranium(III) complexes that bind dinitrogen are known today.[2]Moreover, only very recently the first example of a molecular uranium(III) nitride was reported.[Here, we will present our recent work leading to the reduction of dinitrogen under ambient conditions by fully characterized multimetallic complexes where two uranium(III) cations are held together by a nitride linker or an oxide linker and a flexible metal-ligand framework. We will show that the bound dinitrogen can be further functionalized in mild conditions. Namely, the addition of hydrogen and/or protons or carbon monoxide to the uranium hydrazido complex results in the complete cleavage of dinitrogen with concomitant N-H and N-C bond forming reactions. We will also show how the nature of the linker and of the bound counter-cation affects the reactivity of the uranium centers.

Dinitrogen reduction and fuctionalization by multimetallic uranium complexes

2019 Spring National Meeting

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