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Photochemical Synthesis of Transition Metal-Stabilized Uranium(VI) Nitride Complexes

Author

Listed:
  • Xiaoqing Xin

    (Nanjing University)

  • Iskander Douair

    (Université Paul Sabatier)

  • Thayalan Rajeshkumar

    (Université Paul Sabatier)

  • Yue Zhao

    (Nanjing University)

  • Shuao Wang

    (Soochow University)

  • Laurent Maron

    (Université Paul Sabatier)

  • Congqing Zhu

    (Nanjing University)

Abstract

Uranium nitrides play important roles in dinitrogen activation and functionalization and in chemistry for nuclear fuels, but the synthesis and isolation of the highly reactive uranium(VI) nitrides remains challenging. Here, we report an example of transition metal (TM) stabilized U(VI) nitride complexes, which are generated by the photolysis of azide-bridged U(IV)-TM (TM = Rh, Ir) precursors. The U(V) nitride intermediates with bridged azide ligands are isolated successfully by careful control of the irradiation time, suggesting that the photolysis of azide-bridged U(IV)-TM precursors is a stepwise process. The presence of two U(VI) nitrides stabilized by three TMs is clearly demonstrated by an X-ray crystallographic study. These TM stabilized U(V) nitride intermediates and U(VI) nitride products exhibit excellent stability both in the solid-state and in THF solution under ambient light. Density functional theory calculations show that the photolysis necessary to break the N-N bond of the azide ligands implies excitation from uranium f-orbital to the lowest unoccupied molecular orbital (LUMO), as suggested by the strong antibonding N-(N2) character present in the latter.

Suggested Citation

  • Xiaoqing Xin & Iskander Douair & Thayalan Rajeshkumar & Yue Zhao & Shuao Wang & Laurent Maron & Congqing Zhu, 2022. "Photochemical Synthesis of Transition Metal-Stabilized Uranium(VI) Nitride Complexes," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
  • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-31582-z
    DOI: 10.1038/s41467-022-31582-z
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    References listed on IDEAS

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    1. Marta Falcone & Lucile Chatelain & Rosario Scopelliti & Ivica Živković & Marinella Mazzanti, 2017. "Nitrogen reduction and functionalization by a multimetallic uranium nitride complex," Nature, Nature, vol. 547(7663), pages 332-335, July.
    2. Alexander R. Fox & Suzanne C. Bart & Karsten Meyer & Christopher C. Cummins, 2008. "Towards uranium catalysts," Nature, Nature, vol. 455(7211), pages 341-349, September.
    3. David M. King & Peter A. Cleaves & Ashley J. Wooles & Benedict M. Gardner & Nicholas F. Chilton & Floriana Tuna & William Lewis & Eric J. L. McInnes & Stephen T. Liddle, 2016. "Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes," Nature Communications, Nature, vol. 7(1), pages 1-14, December.
    4. Lucile Chatelain & Elisa Louyriac & Iskander Douair & Erli Lu & Floriana Tuna & Ashley J. Wooles & Benedict M. Gardner & Laurent Maron & Stephen T. Liddle, 2020. "Terminal uranium(V)-nitride hydrogenations involving direct addition or Frustrated Lewis Pair mechanisms," Nature Communications, Nature, vol. 11(1), pages 1-12, December.
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