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Isolation and characterization of a triplet nitrene

Nature Chemistry volume 17, pages 38–43 (2025)Cite this article

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Abstract

Nitrene radical compounds are short-lived intermediates in a variety of nitrogen-involved transformations. They feature either a singlet or a triplet ground state, depending on the electronic properties of the substituents. Triplet nitrenes are highly reactive and their isolation in the condensed phase under ambient conditions is challenging. Here we report the synthesis and isolation of a triplet arylnitrene supported by a bulky hydrindacene ligand. The arylnitrene is fully characterized by various spectroscopic and structural techniques including electron paramagnetic resonance spectroscopy and single-crystal X-ray diffraction. Its high stability is largely attributed to the steric hindrance and effective electron delocalization provided by the supporting ligand. Electron paramagnetic resonance spectroscopy in conjunction with highly correlated wavefunction-based ab initio calculations provides support for a triplet ground state nitrene with axial zero-field splitting D = 0.92 cm–1 and vanishing rhombicity E/D = 0.002.

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Fig. 1: Electronic structures and structurally characterized nitrenes.
Fig. 2: Synthesis and characterization of 2.
Fig. 3: Electronic structure of 2.
Fig. 4: Reactivity studies of nitrene 2.

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Data availability

Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers CCDC 2354664 (Supplementary Data 1), 2354665 (Supplementary Data 2), 2354666 (Supplementary Data 3), 2368517 (Supplementary Data 4), 2354667 (Supplementary Data 5), 2354668 (Supplementary Data 6) and 2368518 (Supplementary Data 7). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All data are available in the main text or Supplementary Information and are also available from the corresponding authors on reasonable request.

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Acknowledgements

The synthetic work was supported by the National Natural Science Foundation of China (grant numbers 22322112, 22488101 and 22071164), and the Suzhou Science & Technology NOVA Program (grant number ZXL2022445). The study of electronic structures was supported by the National Natural Science Foundation of China (grant number 92161204) and the Dalian Institute of Chemical Physics, Chinese Academy of Sciences (grant number DICP I202312). The computational work was supported by the National Supercomputer Center (Tianhe-2 Supercomputer), Guangzhou. We also thank Instrumental Analysis and Research Center, Sun Yat-sen University for the mass spectrometric and elemental analysis.

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Author notes

  1. These authors contributed equally: Dongmin Wang, Wang Chen, Haonan Chen.

Authors and Affiliations

  1. Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, School of Chemistry, IGCME, Sun Yat-sen University, Guangzhou, China

    Dongmin Wang, Haonan Chen, Yizhen Chen, Shengfa Ye & Gengwen Tan

  2. Innovation Center for Chemical Sciences, Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, China

    Dongmin Wang & Haonan Chen

  3. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Wang Chen & Shengfa Ye

  4. University of Chinese Academy of Sciences, Beijing, China

    Wang Chen

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  1. Dongmin Wang
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  3. Haonan Chen
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Contributions

G.T. and S.Y. conceived and supervised the project. D.W., H.C. and Y.C. carried out the experiments. W.C. performed the electronic structure studies.

Corresponding authors

Correspondence to Shengfa Ye or Gengwen Tan.

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The authors declare no competing interests.

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Nature Chemistry thanks Dominik Munz and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–47, Tables 1–3, starting material preparation, experimental procedures and product characterization, and computational details.

Supplementary Data 1

Crystallographic data for 1 (CCDC 2354664).

Supplementary Data 2

Crystallographic data for 2 (CCDC 2354665).

Supplementary Data 3

Crystallographic data for 3 (CCDC 2354666).

Supplementary Data 4

Crystallographic data for 4 (CCDC 2368517).

Supplementary Data 5

Crystallographic data for 5 (CCDC 2354667).

Supplementary Data 6

Crystallographic data for 6 (CCDC 2354668).

Supplementary Data 7

Crystallographic data for 7 (CCDC 2368518).

Supplementary Data 8

Coordinates for the optimized structures.

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Wang, D., Chen, W., Chen, H. et al. Isolation and characterization of a triplet nitrene. Nat. Chem. 17, 38–43 (2025). https://doi.org/10.1038/s41557-024-01669-9

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