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Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings

DOI: 10.1038/s41467-018-04560-7 DOI Help

Authors: Ashley J. Wooles (The University of Manchester) , David P. Mills (University of Manchester) , Floriana Tuna (The University of Manchester) , Eric J. L. Mcinnes (The University of Manchester) , Gareth T. W. Law (The University of Manchester) , Adam J. Fuller (The University of Manchester) , Felipe Kremer (The Australian National University) , Mark Ridgway (The Australian National University) , William Lewis (University of Nottingham) , Laura Gagliardi (University of Minnesota) , Bess Vlaisavljevich (University of Minnesota) , Stephen T. Liddle (The University of Manchester)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Nature Communications , VOL 9

State: Published (Approved)
Published: May 2018
Diamond Proposal Number(s): 9621 , 13559

Open Access Open Access

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 δ-bonded arene bridges. The arenes provide reservoirs that accommodate charge, thus avoiding inter-electronic repulsion that would destabilise these low oxidation state metal-ligand multiple bonds. Using arenes as electronic buffers could constitute a general synthetic strategy by which to stabilise otherwise inherently unstable metal-ligand linkages.

Journal Keywords: Chemical bonding; Coordination chemistry; Inorganic chemistry

Subject Areas: Chemistry


Instruments: I20-Scanning-X-ray spectroscopy (XAS/XES)

Other Facilities: Australian Synchrotron

Documents:
s41467-018-04560-7.pdf