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; Stephen T. Liddle

doi:10.1038/s41467-018-04560-7

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, Stephen T. Liddle

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

53 Scopus citations

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.

Original language	English (US)
Article number	2097
Journal	Nature communications
Volume	9
Issue number	1
DOIs	https://doi.org/10.1038/s41467-018-04560-7
State	Published - Dec 1 2018

Bibliographical note

Funding Information:
We thank the Royal Society (grant UF110005), European Research Council (grants StG239621 and CoG612724), Engineering and Physical Sciences Research Council (grants EP/F030517/1, EP/M027015/1, and EP/P001386/1), Natural Environment Research Council (NE/M014088/1), UK EPSRC National EPR Service, The University of Manchester, and the UK National Nuclear Laboratory for generously supporting this work. Diamond Light Source and the Canberra Australian Synchrotron are thanked for the allocation of XANES beam-time (awards SP9621, SP13559, and M7964). Computational work was supported by the U.S. Department of Energy Director, Office of Basic Energy Sciences (award DE-SC002183) and the High Performance Computing systems of the University of South Dakota. Dr Shu Hayama (Diamond Light Source) and Prof. Sam Shaw (The University of Manchester) are thanked for their assistance with XANES data.

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Wooles, A. J., Mills, D. P., Tuna, F., McInnes, E. J. L., Law, G. T. W., Fuller, A. J., Kremer, F., Ridgway, M., Lewis, W., Gagliardi, L., Vlaisavljevich, B., & Liddle, S. T. (2018). Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings. Nature communications, 9(1), Article 2097. https://doi.org/10.1038/s41467-018-04560-7

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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.",

author = "Wooles, {Ashley J.} and Mills, {David P.} and Floriana Tuna and McInnes, {Eric J.L.} and Law, {Gareth T.W.} and Fuller, {Adam J.} and Felipe Kremer and Mark Ridgway and William Lewis and Laura Gagliardi and Bess Vlaisavljevich and Liddle, {Stephen T.}",

note = "Funding Information: We thank the Royal Society (grant UF110005), European Research Council (grants StG239621 and CoG612724), Engineering and Physical Sciences Research Council (grants EP/F030517/1, EP/M027015/1, and EP/P001386/1), Natural Environment Research Council (NE/M014088/1), UK EPSRC National EPR Service, The University of Manchester, and the UK National Nuclear Laboratory for generously supporting this work. Diamond Light Source and the Canberra Australian Synchrotron are thanked for the allocation of XANES beam-time (awards SP9621, SP13559, and M7964). Computational work was supported by the U.S. Department of Energy Director, Office of Basic Energy Sciences (award DE-SC002183) and the High Performance Computing systems of the University of South Dakota. Dr Shu Hayama (Diamond Light Source) and Prof. Sam Shaw (The University of Manchester) are thanked for their assistance with XANES data. Publisher Copyright: {\textcopyright} 2018 The Author(s).",

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doi = "10.1038/s41467-018-04560-7",

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T1 - Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings

AU - Wooles, Ashley J.

AU - Mills, David P.

AU - Tuna, Floriana

AU - McInnes, Eric J.L.

AU - Law, Gareth T.W.

AU - Fuller, Adam J.

AU - Kremer, Felipe

AU - Ridgway, Mark

AU - Lewis, William

AU - Gagliardi, Laura

AU - Vlaisavljevich, Bess

AU - Liddle, Stephen T.

N1 - Funding Information: We thank the Royal Society (grant UF110005), European Research Council (grants StG239621 and CoG612724), Engineering and Physical Sciences Research Council (grants EP/F030517/1, EP/M027015/1, and EP/P001386/1), Natural Environment Research Council (NE/M014088/1), UK EPSRC National EPR Service, The University of Manchester, and the UK National Nuclear Laboratory for generously supporting this work. Diamond Light Source and the Canberra Australian Synchrotron are thanked for the allocation of XANES beam-time (awards SP9621, SP13559, and M7964). Computational work was supported by the U.S. Department of Energy Director, Office of Basic Energy Sciences (award DE-SC002183) and the High Performance Computing systems of the University of South Dakota. Dr Shu Hayama (Diamond Light Source) and Prof. Sam Shaw (The University of Manchester) are thanked for their assistance with XANES data. Publisher Copyright: © 2018 The Author(s).

PY - 2018/12/1

Y1 - 2018/12/1

N2 - 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.

AB - 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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U2 - 10.1038/s41467-018-04560-7

DO - 10.1038/s41467-018-04560-7

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AN - SCOPUS:85047865392

SN - 2041-1723

VL - 9

JO - Nature communications

JF - Nature communications

IS - 1

M1 - 2097

ER -

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

Abstract

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