Abstract
The oxo groups in the uranyl ion [UO2]2+—one of many oxo cations formed by metals from across the periodic table—are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a ‘Pacman’ environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C–H bond activation reactions are occurring.
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Acknowledgements
We thank the EPSRC(UK), EaStCHEM, the University of Edinburgh and the CEA, CNRS and UPS for support. L.M. is grateful to Institut Universitaire de France. CalMip (CNRS, Toulouse, France), CINES (CNRS, Montpellier, France) and CCRT (CEA, France) are acknowledged for calculation facilities. The authors are grateful to D. Graham, I. Lamour, R. E. Mulvey and S. Robertson for help with obtaining the Raman spectroscopic measurements.
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A.-F.P. and E.H. synthesized and characterized the compounds, and solved the crystal structure data; A.Y. and L.M. carried out the DFT calculations; and S.J.P. solved and refined the disorder components for the crystal structure of 3py. P.L.A. and J.B.L. generated and managed the project, helped characterize the compounds, analysed the data and wrote the manuscript.
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1thf (GIF 1968 kb)
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3py (GIF 3405 kb)
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5thf (GIF 1976 kb)
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Crystallographic data for compound 2thf (CIF 50 kb)
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Crystallographic data for compound 3py (CIF 91 kb)
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Crystallographic data for compound 4py (CIF 68 kb)
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Crystallographic data for compound 5thf (CIF 79 kb)
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Arnold, P., Pécharman, AF., Hollis, E. et al. Uranyl oxo activation and functionalization by metal cation coordination. Nature Chem 2, 1056–1061 (2010). https://doi.org/10.1038/nchem.904
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DOI: https://doi.org/10.1038/nchem.904
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