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  • Back-bonding between an ele...
    Lu, Erli; Atkinson, Benjamin E; Wooles, Ashley J; Boronski, Josef T; Doyle, Laurence R; Tuna, Floriana; Cryer, Jonathan D; Cobb, Philip J; Vitorica-Yrezabal, Inigo J; Whitehead, George F S; Kaltsoyannis, Nikolas; Liddle, Stephen T

    Nature chemistry, 09/2019, Letnik: 11, Številka: 9
    Journal Article

    A fundamental bonding model in coordination and organometallic chemistry is the synergic, donor-acceptor interaction between a metal and a neutral π-acceptor ligand, in which the ligand σ donates to the metal, which π back-bonds to the ligand. This interaction typically involves a metal with an electron-rich, mid-, low- or even negative oxidation state and a ligand with a π* orbital. Here, we report that treatment of a uranium-carbene complex with an organoazide produces a uranium(V)-bis(imido)-dinitrogen complex, stabilized by a lithium counterion. This complex, which was isolated in a crystalline form, involves an electron-poor, high-oxidation-state uranium(V) 5f ion that is π back-bonded to the poor π-acceptor ligand dinitrogen. We propose that this is made possible by a combination of cooperative heterobimetallic uranium-lithium effects and the presence of suitable ancillary ligands that render the uranium ion unusually electron rich. This electron-poor back-bonding could have implications for the field of dinitrogen activation.