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

Ashley J. Wooles, David P. Mills, Floriana Tuna, Eric J. L. McInnes, Gareth T. W. Law, Adam J. Fuller, Felipe Kremer, Mark Ridgway, William Lewis, Laura Gagliardi, Bess Vlaisavljevich () and Stephen T. Liddle ()
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Ashley J. Wooles: The University of Manchester
David P. Mills: The 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

Nature Communications, 2018, vol. 9, issue 1, 1-11

Abstract: 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.

Date: 2018
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DOI: 10.1038/s41467-018-04560-7

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