Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Isolation and characterization of a uranium(VI)–nitride triple bond

This article has been updated

Abstract

The nature and extent of covalency in uranium bonding is still unclear compared with that of transition metals, and there is great interest in studying uranium–ligand multiple bonds. Although U=O and U=NR double bonds (where R is an alkyl group) are well-known analogues to transition-metal oxo and imido complexes, the uranium(VI)–nitride triple bond has long remained a synthetic target in actinide chemistry. Here, we report the preparation of a uranium(VI)–nitride triple bond. We highlight the importance of (1) ancillary ligand design, (2) employing mild redox reactions instead of harsh photochemical methods that decompose transiently formed uranium(VI) nitrides, (3) an electrostatically stabilizing sodium ion during nitride installation, (4) selecting the right sodium sequestering reagent, (5) inner versus outer sphere oxidation and (6) stability with respect to the uranium oxidation state. Computational analyses suggest covalent contributions to U≡N triple bonds that are surprisingly comparable to those of their group 6 transition-metal nitride counterparts.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Figure 1: Synthesis of compounds 59 from precursors 14.
Figure 2: Molecular structures of 7, 8, 12 and 13.
Figure 3: Mechanism for the photochemical conversion of 9 into 7 into 8.
Figure 4: Synthesis of compounds 1013 from precursors 2 and 3.
Figure 5: The top three occupied α-spin Kohn–Sham MOs of 7 (hydrogen atoms omitted for clarity).

Change history

  • 10 May 2013

    In the version of this Article originally published online, in the second paragraph of the section 'Synthetic considerations for preparing U≡N triple bonds', compound 7 was referred to instead of compound 12. The relevant text should have read 'The characterization data for 12 fully support its formulation (Supplementary Information). The crystal structure of 12 (Fig. 2c) reveals...' This has been corrected in the HTML and PDF versions of the Article.

References

  1. 1

    Nugent, W. A. & Mayer, J. M. Metal–Ligand Multiple Bonds (Wiley, 1988).

    Google Scholar 

  2. 2

    Giesbrecht, G. R. & Gordon, J. C. Lanthanide alkylidene and imido complexes. Dalton Trans. 2387–2393 (2004).

  3. 3

    Summerscales, O. T. & Gordon, J. C. Complexes containing multiple bonding interactions between lanthanoid elements and main-group fragments. RSC Adv. http://dx.doi.org/10.1039/C3RA23151H (2013).

  4. 4

    Ephritikhine, M. The vitality of uranium molecular chemistry at the dawn of the XXIst century. Dalton Trans. 2501–2516 (2006).

  5. 5

    Hayton, T. W. Metal–ligand multiple bonding in uranium: structure and reactivity. Dalton Trans. 39, 1145–1158 (2010).

    CAS  Article  Google Scholar 

  6. 6

    Hayton, T. W. Recent developments in actinide–ligand multiple bonding. Chem. Commun. 49, 2956–2973 (2013).

    CAS  Article  Google Scholar 

  7. 7

    Castro-Rodríguez, I. & Meyer, K. Small molecule activation at uranium coordination complexes: control of reactivity via molecular architecture. Chem. Commun. 1353–1368 (2006).

  8. 8

    Lam, O. P., Anthon, C. & Meyer, K. Influence of steric pressure on the activation of carbon dioxide and related small molecules by uranium coordination complexes. Dalton Trans. 9677–9691 (2009).

  9. 9

    Fox, A. R., Bart, S. C., Meyer, K. & Cummins, C. C. Towards uranium catalysts. Nature 455, 341–349 (2008).

    CAS  Article  Google Scholar 

  10. 10

    Cooper, O. J. et al. Uranium–carbon multiple bonding: facile access to the pentavalent uranium carbene [U{C(PPh2NSiMe3)2}(Cl)2(I)] and comparison of UV=C and UIV=C double bonds. Angew. Chem. Int. Ed. 50, 2383–2386 (2011).

    CAS  Article  Google Scholar 

  11. 11

    Mills, D. P. et al. Synthesis of a uranium(VI) carbene: reductive formation of uranyl(V) methanides, oxidative preparation of a [R2C=U=O]2+ analogue of the [O=U=O]2+ uranyl ion (R = Ph2PNSiMe3), and comparison of the nature of UIV=C, UV=C and UVI=C double bonds. J. Am. Chem. Soc. 134, 10047–10054 (2012).

    CAS  Article  Google Scholar 

  12. 12

    Cantat, T. et al. The U=C double bond: synthesis and study of uranium nucleophilic carbene complexes. J. Am. Chem. Soc. 131, 963–972 (2009).

    CAS  Article  Google Scholar 

  13. 13

    Tourneux, J-C. et al. Exploring the uranyl organometallic chemistry: from single to double uranium–carbon bonds. J. Am. Chem. Soc. 133, 6162–6165 (2011).

    CAS  Article  Google Scholar 

  14. 14

    Fortier, S., Walensky, J. R., Wu, G. & Hayton, T. W. Synthesis of a phosphorano-stabilized U(IV) carbene via one-electron oxidation of a U(III)–ylide adduct. J. Am. Chem. Soc. 133, 6894–6897 (2011).

    CAS  Article  Google Scholar 

  15. 15

    Brown, J. L., Fortier, S., Lewis, R. A., Wu, G. & Hayton, T. W. A complete family of terminal uranium chalcogenides, [U(E)(N{SiMe3}2)3] (E = O, S, Se, Te). J. Am. Chem. Soc. 134, 15468–15475 (2012).

    CAS  Article  Google Scholar 

  16. 16

    Streit, M. & Ingold, F. Nitrides as a nuclear fuel option. J. Eur. Ceram. Soc. 25, 2687–2692 (2005).

    CAS  Article  Google Scholar 

  17. 17

    Chinthaka Silva, G. W. et al. Reaction sequence and kinetics of uranium nitride decomposition. Inorg. Chem. 48, 10635–10642 (2009).

    Article  Google Scholar 

  18. 18

    Kempter, C. P., McGuire, J. C. & Nadler, M. R. Uranium mononitride. Anal. Chem. 31, 156–157 (1959).

    CAS  Article  Google Scholar 

  19. 19

    Green, D. W. & Reedy, G. T. The identification of UN in Ar matrices. J. Chem. Phys. 65, 2921–2922 (1976).

    CAS  Article  Google Scholar 

  20. 20

    Hunt, R. D., Yustein, J. T. & Andrews, L. Matrix infrared spectra of NUN formed by the insertion of uranium atoms into molecular nitrogen. J. Chem. Phys. 98, 6070–6074 (1993).

    CAS  Article  Google Scholar 

  21. 21

    Andrews, L., Wang, X., Lindh, R., Roos, B. O. & Marsden, C. J. Simple N≡UF3 and P≡UF3 molecules with triple bonds to uranium. Angew. Chem. Int. Ed. 47, 5366–5370 (2008).

    CAS  Article  Google Scholar 

  22. 22

    Wang, X., Andrews, L., Vlaisavljevich, B. & Gagliardi, L. Combined triple and double bonds to uranium: the N≡U=N–H uranimine nitride molecule prepared in solid argon. Inorg. Chem. 50, 3826–3831 (2011).

    CAS  Article  Google Scholar 

  23. 23

    Zhou, M. & Andrews, L. Infrared spectra and pseudopotential calculations for NUO+, NUO, and NThO in solid neon. J. Chem. Phys. 111, 11044–11049 (1999).

    CAS  Article  Google Scholar 

  24. 24

    Heinemann, C. & Schwarz, H. NUO+, a new species isoelectronic to the uranyl dication UO22+. Chem. Eur. J. 1, 7–11 (1995).

    CAS  Article  Google Scholar 

  25. 25

    Pyykkö, P., Li, J. & Runeberg, N. Quasirelativistic pseudopotential study of species isoelectronic to uranyl and the equatorial coordination of uranyl. J. Phys. Chem. 98, 4809–4813 (1994).

    Article  Google Scholar 

  26. 26

    Korobkov, I., Gambarotta, S. & Yap, G. P. A. A highly reactive uranium complex supported by the calix[4]tetrapyrrole tetraanion affording dinitrogen cleavage, solvent deoxygenation, and polysilanol depolymerization. Angew. Chem. Int. Ed. 41, 3433–3436 (2002).

    CAS  Article  Google Scholar 

  27. 27

    Evans, W. J., Kozimor, S. A. & Ziller, J. W. Molecular octa-uranium rings with alternating nitride and azide bridges. Science 309, 1835–1838 (2005).

    CAS  Article  Google Scholar 

  28. 28

    Evans, W. J., Miller, K. A., Ziller, J. W. & Greaves, J. Analysis of uranium azide and nitride complexes by atmospheric pressure chemical ionization mass spectrometry. Inorg. Chem. 46, 8008–8018 (2007).

    CAS  Article  Google Scholar 

  29. 29

    Nocton, G., Pécaut, J. & Mazzanti, M. A nitrido-centered uranium azido cluster obtained from a uranium azide. Angew. Chem. Int. Ed. 47, 3040–3042 (2008).

    CAS  Article  Google Scholar 

  30. 30

    Fox, A. R., Arnold, P. L. & Cummins, C. C. Uranium–nitrogen multiple bonding: isostructural anionic, neutral, and cationic uranium nitride complexes featuring a linear U=N=U core. J. Am. Chem. Soc. 132, 3250–3251 (2010).

    CAS  Article  Google Scholar 

  31. 31

    Fortier, S., Wu, G. & Hayton, T. W. Synthesis of a nitrido-substituted analogue of the uranyl ion, [N=U=O]+. J. Am. Chem. Soc. 132, 6888–6889 (2010).

    CAS  Article  Google Scholar 

  32. 32

    Fox, A. R. & Cummins, C. C. Uranium–nitrogen multiple bonding: the case of a four-coordinate uranium(VI) nitridoborate complex. J. Am. Chem. Soc. 131, 5716–5717 (2009).

    CAS  Article  Google Scholar 

  33. 33

    Thomson, R. K. et al. Uranium azide photolysis results in C–H bond activation and provides evidence for a terminal uranium nitride. Nature Chem. 2, 723–729 (2010).

    CAS  Article  Google Scholar 

  34. 34

    King, D. M. et al. Synthesis and structure of a terminal uranium nitride complex. Science 337, 717–720 (2012).

    CAS  Article  Google Scholar 

  35. 35

    Denning, R. G. Electronic structure and bonding in actinyl ions. Struct. Bonding (Berl.) 79, 215–276 (1992).

    CAS  Article  Google Scholar 

  36. 36

    Kaltsoyannis, N. Computational study of analogues of the uranyl ion containing the –N=U=N– unit: density functional theory calculations on UO22+, UON+, UN2, UO(NPH3)3+, U(NPH3)24+, [UCl4{NPR3}2] (R = H, Me), and [UOCl4{NP(C6H5)3}]. Inorg. Chem. 39, 6009–6017 (2000).

    CAS  Article  Google Scholar 

  37. 37

    Kosog, B., La Pierre, H. S., Heinemann, F. W., Liddle, S. T. & Meyer, K. Synthesis of uranium(VI) terminal oxo complexes: molecular geometry driven by the inverse trans-influence. J. Am. Chem. Soc. 134, 5284–5289 (2012).

    CAS  Article  Google Scholar 

  38. 38

    Mills, D. P. et al. A delocalized arene-bridged diuranium single-molecule magnet. Nature Chem. 3, 454–460 (2011).

    CAS  Article  Google Scholar 

  39. 39

    Lam, O. P., Heinemann, F. W. & Meyer, K. Activation of elemental S, Se and Te with uranium(III): bridging U–E–U (E = S, Se) and diamond-core complexes U–(E)2–U (E = O, S, Se, Te). Chem. Sci. 2, 1538–1547 (2011).

    CAS  Article  Google Scholar 

  40. 40

    Kramer, G. M., Dines, M. B., Kaldor, A., Hall, R. & McClure, D. Photochemical behavior of a uranyl bis(hexafluoroacetylacetonate)–tetrahydrofuran complex. 1. Inorg. Chem. 20, 1421–1426 (1981).

    CAS  Article  Google Scholar 

  41. 41

    Natrajan, L. S. Developments in the photophysics and photochemistry of actinide ions and their coordination compounds. Coord. Chem. Rev. 256, 1583–1603 (2012).

    CAS  Article  Google Scholar 

  42. 42

    Zi, G. et al. Preparation and reactions of base-free bis(1,2,4-tri-tert-butylcyclopentadienyl)uranium oxide, Cp′2UO. Organometallics 24, 4251–4264 (2005).

    CAS  Article  Google Scholar 

  43. 43

    Bailey, P. J. et al. The first structural characterisation of a group 2 metal alkylperoxide complex: comments on the cleavage of dioxygen by magnesium alkyl complexes. Chem. Eur. J. 9, 4820–4828 (2003).

    CAS  Article  Google Scholar 

  44. 44

    Graves, C. R. & Kiplinger, J. L. Pentavalent uranium chemistry – synthetic pursuit of a rare oxidation state. Chem. Commun. 3831–3853 (2009).

  45. 45

    Hayton, T. W. et al. Synthesis of imido analogs of the uranyl ion. Science 310, 1941–1943 (2005).

    CAS  Article  Google Scholar 

  46. 46

    Zalkin, A., Brennan, J. G. & Andersen, R. A. Tris[bis(trimethylsilyl)amido](trimethylsilylimido)uranium(V). Acta Cryst. C 44, 1553–1554 (1988).

    Article  Google Scholar 

  47. 47

    Burns, C. J., Smith, W. H., Huffman, J. C. & Sattelberger, A. P. Uranium(VI) organoimido complexes. J. Am. Chem. Soc. 112, 3237–3239 (1990).

    CAS  Article  Google Scholar 

  48. 48

    Arney, D. S., Burns, C. J. & Smith, D. C. Synthesis and structure of the first uranium(VI) organometallic complex. J. Am. Chem. Soc. 114, 10068–10069 (1992).

    CAS  Article  Google Scholar 

  49. 49

    Odom, A. L. & Cummins, C. C. Nitric oxide cleavage: synthesis of terminal chromium(VI) nitride complexes via nitrosyl deoxygenation. J. Am. Chem. Soc. 117, 6613–6614 (1995).

    CAS  Article  Google Scholar 

  50. 50

    Curley, J. J., Cook, T. R., Reece, S. Y., Müller, P. & Cummins, C. C. Shining light on dinitrogen cleavage: structural features, redox chemistry, and photochemistry of the key intermediate bridging dinitrogen complex. J. Am. Chem. Soc. 130, 9394–9405 (2008).

    CAS  Article  Google Scholar 

  51. 51

    Clough, C. R. et al. Organic nitriles from acid chlorides: an isovalent N for (O)Cl exchange reaction mediated by a tungsten nitride complex. J. Am. Chem. Soc. 126, 7742–7743 (2004).

    CAS  Article  Google Scholar 

  52. 52

    Pepper, M. & Bursten, B. E. The electronic structure of actinide-containing molecules: a challenge to applied quantum chemistry. Chem. Rev. 91, 719–741 (1991).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

We are grateful to the European Research Council, the UK Engineering and Physical Sciences Research Council, including the National UK Electron Paramagnetic Resonance Facility at Manchester, the University of Nottingham and the UK National Nuclear Laboratory for generous funding and support, the Royal Society for the award of a University Research Fellowship (S.T.L.) and European Cooperation in Science and Technology (COST) Action CM1006 for support.

Author information

Affiliations

Authors

Contributions

D.M.K. synthesized and characterized the compounds. F.T. and E.J.L.M. recorded and analysed the electron paramagnetic resonance data. J.M. carried out and analysed the DFT calculations. W.L. and A.J.B. carried out the X-ray single-crystal structure analyses. S.T.L. originated the central idea, supervised the work, analysed the data and wrote the manuscript with contributions from all the co-authors.

Corresponding author

Correspondence to Stephen T. Liddle.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Rights and permissions

Reprints and Permissions

About this article

Cite this article

King, D., Tuna, F., McInnes, E. et al. Isolation and characterization of a uranium(VI)–nitride triple bond. Nature Chem 5, 482–488 (2013). https://doi.org/10.1038/nchem.1642

Download citation

Further reading

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing