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

Xiaoqing Xin, Iskander Douair, Thayalan Rajeshkumar, Yue Zhao, Shuao Wang, Laurent Maron () and Congqing Zhu ()
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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

Nature Communications, 2022, vol. 13, issue 1, 1-9

Abstract: 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.

Date: 2022
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DOI: 10.1038/s41467-022-31582-z

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