Journal article
Uranium(III)-carbon multiple bonding supported by arene delta-bonding in mixed-valence hexauranium nanometre-scale rings
Nature communications, Vol.9(1), 2097
05/29/2018
DOI: 10.1038/s41467-018-04560-7
PMCID: PMC5974406
PMID: 29844376
Abstract
Despite the fact that non-aqueous uranium chemistry is over 60 years old, most polarised-covalent uranium-element multiple bonds involve formal uranium oxidation states IV, V, and VI. The paucity of uranium(III) congeners is because, in common with metal-ligand multiple bonding generally, such linkages involve strongly donating, charge-loaded ligands that bind best to electron-poor metals and inherently promote disproportionation of uranium(III). Here, we report the synthesis of hexauranium-methanediide nanometre-scale rings. Combined experimental and computational studies suggest overall the presence of formal uranium(III) and (IV) ions, though electron delocalisation in this Kramers system cannot be definitively ruled out, and the resulting polarised-covalent U = C bonds are supported by iodide and delta-bonded arene bridges. The arenes provide reservoirs that accommodate charge, thus avoiding inter-electronic repulsion that would destabilise these low oxidation state metalligand multiple bonds. Using arenes as electronic buffers could constitute a general synthetic strategy by which to stabilise otherwise inherently unstable metal-ligand linkages.
Details
- Title: Subtitle
- Uranium(III)-carbon multiple bonding supported by arene delta-bonding in mixed-valence hexauranium nanometre-scale rings
- Creators
- Ashley J. Wooles - University of ManchesterDavid P. Mills - University of ManchesterFloriana Tuna - University of ManchesterEric J. L. McInnes - University of ManchesterGareth T. W. Law - University of ManchesterAdam J. Fuller - University of ManchesterFelipe Kremer - Australian National UniversityMark Ridgway - Australian National UniversityWilliam Lewis - University of NottinghamLaura Gagliardi - University of MinnesotaBess Vlaisavljevich - University of MinnesotaStephen T. Liddle - University of Manchester
- Resource Type
- Journal article
- Publication Details
- Nature communications, Vol.9(1), 2097
- Publisher
- Springer Nature
- DOI
- 10.1038/s41467-018-04560-7
- PMID
- 29844376
- PMCID
- PMC5974406
- ISSN
- 2041-1723
- eISSN
- 2041-1723
- Number of pages
- 11
- Grant note
- NE/M014088/1 / Natural Environment Research Council; UK Research & Innovation (UKRI); Natural Environment Research Council (NERC) UK EPSRC National EPR Service; UK Research & Innovation (UKRI); Engineering & Physical Sciences Research Council (EPSRC) NE/M014088/1 / NERC; UK Research & Innovation (UKRI); Natural Environment Research Council (NERC) UF110005 / Royal Society UK National Nuclear Laboratory SP9621; SP13559; M7964 / Diamond Light Source StG239621; CoG612724 / European Research Council; European Research Council (ERC) EP/F030517/1; EP/M027015/1; EP/P001386/1 / Engineering and Physical Sciences Research Council; UK Research & Innovation (UKRI); Engineering & Physical Sciences Research Council (EPSRC) University of Manchester EP/M027015/1; EP/P001386/1 / EPSRC; UK Research & Innovation (UKRI); Engineering & Physical Sciences Research Council (EPSRC) DE-SC002183 / U.S. Department of Energy, Office of Basic Energy Sciences; United States Department of Energy (DOE) SP9621; SP13559; M7964 / Canberra Australian Synchrotron
- Language
- English
- Date published
- 05/29/2018
- Academic Unit
- Chemistry
- Record Identifier
- 9984618512002771
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