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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.
- Source :
-
Nature chemistry [Nat Chem] 2019 Sep; Vol. 11 (9), pp. 806-811. Date of Electronic Publication: 2019 Aug 19. - Publication Year :
- 2019
-
Abstract
- 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 <superscript>1</superscript> 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.
Details
- Language :
- English
- ISSN :
- 1755-4349
- Volume :
- 11
- Issue :
- 9
- Database :
- MEDLINE
- Journal :
- Nature chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 31427765
- Full Text :
- https://doi.org/10.1038/s41557-019-0306-x