期刊
NATURE COMMUNICATIONS
卷 9, 期 -, 页码 -出版社
NATURE PUBLISHING GROUP
DOI: 10.1038/s41467-018-04560-7
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资金
- Royal Society [UF110005]
- European Research Council [StG239621, CoG612724]
- Engineering and Physical Sciences Research Council [EP/F030517/1, EP/M027015/1, EP/P001386/1]
- Natural Environment Research Council [NE/M014088/1]
- UK EPSRC National EPR Service
- University of Manchester
- UK National Nuclear Laboratory
- Diamond Light Source [SP9621, SP13559, M7964]
- Canberra Australian Synchrotron [SP9621, SP13559, M7964]
- U.S. Department of Energy, Office of Basic Energy Sciences [DE-SC002183]
- EPSRC [EP/P001386/1, EP/M027015/1] Funding Source: UKRI
- NERC [NE/M014088/1] Funding Source: UKRI
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.
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