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

Lookup NU author(s): Dr Erli Lu, Dr Stephen Liddle

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This is the authors' accepted manuscript of an article that has been published in its final definitive form by Nature Publishing Group, 2019.

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Abstract

© 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.


Publication metadata

Author(s): Lu E, Atkinson BE, Wooles AJ, Boronski JT, Doyle LR, Tuna F, Cryer JD, Cobb PJ, Vitorica-Yrezabal IJ, Whitehead GFS, Kaltsoyannis N, Liddle ST

Publication type: Article

Publication status: Published

Journal: Nature Chemistry

Year: 2019

Volume: 11

Issue: 9

Pages: 806-811

Print publication date: 01/09/2019

Online publication date: 19/08/2019

Acceptance date: 08/07/2019

Date deposited: 03/10/2019

ISSN (print): 1755-4330

ISSN (electronic): 1755-4349

Publisher: Nature Publishing Group

URL: https://doi.org/10.1038/s41557-019-0306-x

DOI: 10.1038/s41557-019-0306-x

PubMed id: 31427765


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