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

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.

Authors:
 [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [2];  [2]; ORCiD logo [3];  [4]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Manchester (United Kingdom)
  2. Australian National Univ., Canberra, ACT (Australia)
  3. Univ. of Nottingham (United Kingdom)
  4. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1506462
Grant/Contract Number:  
SC0002183
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY

Citation Formats

Wooles, Ashley J., Mills, David P., Tuna, Floriana, McInnes, Eric J. L., Law, Gareth T. W., Fuller, Adam J., Kremer, Felipe, Ridgway, Mark, Lewis, William, Gagliardi, Laura, Vlaisavljevich, Bess, and Liddle, Stephen T. Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings. United States: N. p., 2018. Web. doi:10.1038/s41467-018-04560-7.
Wooles, Ashley J., Mills, David P., Tuna, Floriana, McInnes, Eric J. L., Law, Gareth T. W., Fuller, Adam J., Kremer, Felipe, Ridgway, Mark, Lewis, William, Gagliardi, Laura, Vlaisavljevich, Bess, & Liddle, Stephen T. Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings. United States. doi:10.1038/s41467-018-04560-7.
Wooles, Ashley J., Mills, David P., Tuna, Floriana, McInnes, Eric J. L., Law, Gareth T. W., Fuller, Adam J., Kremer, Felipe, Ridgway, Mark, Lewis, William, Gagliardi, Laura, Vlaisavljevich, Bess, and Liddle, Stephen T. Tue . "Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings". United States. doi:10.1038/s41467-018-04560-7. https://www.osti.gov/servlets/purl/1506462.
@article{osti_1506462,
title = {Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings},
author = {Wooles, Ashley J. and Mills, David P. and Tuna, Floriana and McInnes, Eric J. L. and Law, Gareth T. W. and Fuller, Adam J. and Kremer, Felipe and Ridgway, Mark and Lewis, William and Gagliardi, Laura and Vlaisavljevich, Bess and Liddle, Stephen T.},
abstractNote = {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.},
doi = {10.1038/s41467-018-04560-7},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {5}
}

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