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Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions

Nature Chemistry volume 9, pages 850–855 (2017)Cite this article

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Abstract

Actinyl species, [AnO2]2+, are well-known derivatives of the f-block because of their natural occurrence and essential roles in the nuclear fuel cycle. Along with their nitrogen analogues, [An(NR)2]2+, actinyls are characterized by their two strong trans-An–element multiple bonds, a consequence of the inverse trans influence. We report that these robust bonds can be weakened significantly by increasing the number of multiple bonds to uranium, as demonstrated by a family of uranium(VI) dianions bearing four U–N multiple bonds, [M]2[U(NR)4] (M = Li, Na, K, Rb, Cs). Their geometry is dictated by cation coordination and sterics rather than by electronic factors. Multiple bond weakening by the addition of strong π donors has the potential for applications in the processing of high-valent actinyls, commonly found in environmental pollutants and spent nuclear fuels.

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Figure 1: Schematic diagram showing the progression of decreasing bond order in uranium imido species as additional imido substituents are added.
Figure 2: Chemical equation that describes the synthetic procedures for the generation of 2-Li to 2-Cs from U(NDIPP)3(THF)3.
Figure 3: Molecular structures for the tetrakis(imido)uranate(VI) dianions.
Figure 4: DFT calculations for tetrakis(imido)uranate(VI) dianions.

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Acknowledgements

This work was funded by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the US Department of Energy (DOE) through Grants DE-SC0008479 (S.C.B.) and USDOE/DESC002183 (L.G., J.X. and D.R.). L.G. used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US DOE under contract no. DE-AC02-05CH11231. The Prospector X-ray diffractometer was funded by NSF Grant DMR 1337296. We thank S. Odoh for useful discussion.

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Authors and Affiliations

  1. Department of Chemistry, H.C. Brown Laboratory, Purdue University, West Lafayette, 47907, Indiana, USA

    Nickolas H. Anderson, Matthias Zeller & Suzanne C. Bart

  2. Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, Minneapolis, 55455, Minnesota, USA

    Jing Xie, Debmalya Ray & Laura Gagliardi

  3. Department of Chemistry, Youngstown State University, Youngstown, 44555, Ohio, USA

    Matthias Zeller

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Contributions

N.H.A. and S.C.B. conceived and designed the experiments. N.H.A. synthesized all the compounds. J.X., D.R. and L.G. performed the computations. N.H.A. and M.Z. performed the crystallographic analysis. N.H.A., J.X. and S.C.B. co-wrote the manuscript.

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Correspondence to Suzanne C. Bart.

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Supplementary information

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Supplementary information (PDF 5278 kb)

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Crystallographic data for compound 2-Na (CIF 746 kb)

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Crystallographic data for compound 2-Rb (CIF 571 kb)

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Crystallographic data for compound 2-Cs (CIF 1111 kb)

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Crystallographic data for compound 2-K(crypt) (CIF 1308 kb)

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Crystallographic data for compound 2-K (CIF 4986 kb)

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Anderson, N., Xie, J., Ray, D. et al. Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions. Nature Chem 9, 850–855 (2017). https://doi.org/10.1038/nchem.2767

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