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

Nature Communications
Ashley J WoolesStephen T Liddle

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.

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Citations

Sep 2, 2018·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Meng TangGuochun Yang
Apr 25, 2020·Angewandte Chemie·Holger BraunschweigMuralee Murugesu
Sep 10, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Sayantani Saha, Moris S Eisen
Nov 28, 2018·Nature Communications·Wei SuCongqing Zhu
Oct 13, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael A Boreen, John Arnold
Feb 13, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Lei ZhangShaodan Li
Mar 5, 2021·Inorganic Chemistry·Polly L ArnoldGary S Nichol
Apr 30, 2021·Chemistry : a European Journal·Wei SuQing Ye
Dec 15, 2020·Journal of the American Chemical Society·Chao YuWenliang Huang
Mar 21, 2019·Journal of the American Chemical Society·Michael A BoreenJohn Arnold
Jun 14, 2019·Chemical Reviews·Marie Fustier-BoutignonNicolas Mézailles

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Methods Mentioned

BETA
X-ray
NMR

Software Mentioned

Molcas
QTAIM
RASSCF
CASPT2

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