Atkinson BE

Boronski JT

Cobb PJ

Cryer JD

Doyle LR

Kaltsoyannis N

Liddle ST

Lu E

Tuna F

Vitorica-Yrezabal IJ

Whitehead GFS

Wooles AJ

\ua9 2019, The Author(s), under exclusive licence to Springer Nature Limited.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) 5f1 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

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Back-bonding between an electron-poor, high-oxidation-state metal and poor <em>π</em>-acceptor ligand in a uranium(v)–dinitrogen complex

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Back-bonding between an electron-poor, high-oxidation-state metal and poor <em>π</em>-acceptor ligand in a uranium(v)–dinitrogen complex

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