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A crystalline dithorium complex with a Th–Th bond

Nature Synthesis (2025)Cite this article

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Abstract

Theoretical studies predict that homoatomic metal–metal bonds of f-block actinide elements should be ubiquitous. Surprisingly, however, the isolation and characterization of compounds featuring an actinide–actinide bond has proven challenging and the field remains undeveloped. Here we report a well-defined thorium dimer featuring a Th–Th two-centre one-electron (2c-1e) σ bond and a 2c-1e π bond. This thorium dimer was synthesized by reducing a Th(IV) chloride complex with potassium metal in tetrahydrofuran. Magnetic measurements indicate that this thorium dimer features exceedingly strong antiferromagnetic coupling between the two formal Th(III) centres with a coupling constant J ≤ −1,200 cm−1 such that the Th–Th interaction has covalent bond character. Detailed computational investigations further support the existence of the Th–Th bond in this molecule. These results demonstrate that diactinide complexes with actinide–actinide bonds are accessible but require an appropriate ligand framework to stabilize low-valent actinide centres.

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Fig. 1: Synthesis and reactivity of complex 2.
Fig. 2: Molecular structures of complex 2.
Fig. 3: Magnetometric measurements and energy scheme for two doublet Th(III) centres.
Fig. 4: Theoretical study of complex 2.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request. The X-ray crystallographic coordinates for structures reported in this study have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition numbers CCDC 2182247 (2) and 2182248 (3). These CCDC data can be obtained free of charge via the CCDC at www.ccdc.cam.ac.uk/data_request/cif.

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Acknowledgements

The work in Dalian is supported by the National Natural Science Foundation of China (grant nos. 92161204 and 92461311, S.Y.) and Dalian Institute of Chemical Physics, Chinese Academy of Sciences (grant no. DICP I202312, S.Y.). The work in Nanjing is supported by the National Key R&D Program of China (grant no. 2021YFA1502500, C.Z.), the National Natural Science Foundation of China (grant no. 22271138, C.Z.), the Natural Science Foundation of Jiangsu Province (grant no. BK20220065, C.Z.) and the Fundamental Research Funds for the Central Universities (grant no. 020514380329, C.Z.). L.M. is a member of the Institute Universitaire de France. Humboldt Foundation and Chinese Academy of Science are acknowledged for support. CalMip is also gratefully acknowledged for a generous grant of computing time.

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Author notes

  1. These authors contributed equally: Weiming Sheng, Fei Xie.

Authors and Affiliations

  1. State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China

    Weiming Sheng, Yue Zhao, Yufei Jiang & Congqing Zhu

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

    Fei Xie, Wang Chen & Shengfa Ye

  3. LPCNO, CNRS and INSA, Université Paul Sabatier, Toulouse, France

    Thayalan Rajeshkumar & Laurent Maron

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

    Wang Chen

  5. 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

    Shengfa Ye

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  1. Weiming Sheng
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Contributions

C.Z. conceived this project. W.S. performed the synthesis experiments. F.X., W.C. and Y.Z. performed the SQUID and X-ray diffraction experiments. W.S. and Y.J. performed HRMS experiments. C.Z. and S.Y. analysed the experimental data. T.R. conducted the theoretical computations, and L.M. analysed the results. C.Z., S.Y. and L.M. drafted the paper. All authors discussed the results and contributed to the preparation of the final paper.

Corresponding authors

Correspondence to Shengfa Ye, Laurent Maron or Congqing Zhu.

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Nature Synthesis thanks Pekka Pyykkö, Weiqun Shi and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Experimental details, Supplementary Figs. 1–44 and Tables 1–18.

Supplementary Data 1

X-ray crystallographic data for 2, CCDC 2182247.

Supplementary Data 2

X-ray crystallographic data for 3, CCDC 2182248.

Source data

Source Data Fig. 3

Source data of unprocessed magnetometric measurements.

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Sheng, W., Xie, F., Rajeshkumar, T. et al. A crystalline dithorium complex with a Th–Th bond. Nat. Synth (2025). https://doi.org/10.1038/s44160-025-00789-5

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