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Radical ligand transfer catalysis of photoexcited dinuclear gold complexes

Nature Catalysis volume 9, pages 18–27 (2026)Cite this article

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Abstract

Radical ligand transfer (RLT), a process in which alkyl radicals capture ligands from high-valent metal species, has emerged as a powerful synthetic approach in organic chemistry. While RLT processes mediated by 3d transition metals have been developed, the application of 5d transition metals remains underexplored due to the limited flexibility in their oxidation states. Here we present a catalytic approach leveraging sequential photoinduced electron transfer in dinuclear gold complexes to achieve an efficient RLT process. This strategy facilitates formal additions of gem-dichloroalkanes and Freon-22 bearing unactivated C(sp3)–Cl bonds to different kinds of alkenes, with high reactivity, excellent atom economy and broad scope. Combined mechanistic and theoretical investigations reveal a latent AuIIAuII pathway. The success originates from sequential excitation of dinuclear gold complexes for the formation of a covalent Au–Au bond, which can markedly weaken the Au–Cl bond and facilitate ligand transfer.

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Fig. 1: Challenges and strategies of radical ligand transfer catalysis of gold complexes.
Fig. 2: Optimization of reaction conditions.
Fig. 3: Control experiments for mechanistic studies.
Fig. 4: Computational mechanistic studies and proposed mechanisms.
Fig. 5: Substrate scope of alkenes.
Fig. 6: Substrate scope of alkenes with Freon-22.

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Data availability

The data supporting the findings of this study are available in the paper and its Supplementary Information or from the corresponding authors upon request.

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Acknowledgements

We thank National Natural Science Foundation of China (22471121, 22471122, 22271144), National Key Research and Development Program of China (2022YFA150320), the Fundamental Research Funds for the Central Universities (grant no. 0020514380327) and the Open Project of State Key Laboratory of Natural Medicines (SKLNMKF202401) for financial support. All theoretical calculations were performed at the High-Performance Computing Center (HPCC) of Nanjing University. We thank W. Wang, Q. Fang, B. Ling and G. Dong at Nanjing University for reproduction of the experimental procedures for products 33, 18, 59 and 64.

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Author notes

  1. These authors contributed equally: Yaohang Cheng, Chengyihan Gu.

Authors and Affiliations

  1. State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), Center for Shared Scientific Research Facilities (CSSRF), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China

    Yaohang Cheng, Chengyihan Gu, Jie Han, Yulan Chen, Yuxi Tian, Chengjian Zhu & Jin Xie

  2. Key Laboratory of Material Simulation Methods and Software of Ministry of Education, College of Physics, Jilin University, Changchun, China

    Jie Han

  3. State Key Laboratory of Natural Medicines, China Pharmaceutical University, Nanjing, China

    Jin Xie

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  1. Yaohang Cheng
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Contributions

J.X. conceived the work and designed the experiments. Y. Cheng, Y. Chen, Y.T and C.Z. performed the experiments and analysed the experimental data. C.G. performed the density functional theory calculations and discussed the results with J.H., and J.X. co-wrote the paper with input from all the other authors.

Corresponding authors

Correspondence to Jie Han or Jin Xie.

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Nature Catalysis 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. 1–218 and Tables 1–4.

Supplementary Data 1

Cartesian coordinates of all the optimized geometries.

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Cheng, Y., Gu, C., Han, J. et al. Radical ligand transfer catalysis of photoexcited dinuclear gold complexes. Nat Catal 9, 18–27 (2026). https://doi.org/10.1038/s41929-025-01462-y

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