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Transition-metal-bridged bimetallic clusters with multiple uranium–metal bonds

Nature Chemistry volume 11, pages 248–253 (2019)Cite this article

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Abstract

Heterometallic clusters are important in catalysis and small-molecule activation because of the multimetallic synergistic effects from different metals. However, multimetallic species that contain uranium–metal bonds remain very scarce due to the difficulties in their synthesis. Here we present a straightforward strategy to construct a series of heterometallic clusters with multiple uranium–metal bonds. These complexes were created by facile reactions of a uranium precursor with Ni(COD)2 (COD, cyclooctadiene). The multimetallic clusters’ cores are supported by a heptadentate N4P3 scaffold. Theoretical investigations indicate the formation of uranium–nickel bonds in a U2Ni2 and a U2Ni3 species, but also show that they exhibit a uranium–uranium interaction; thus, the electronic configuration of uranium in these species is U(iii)-5f26d1. This study provides further understanding of the bonding between f-block elements and transition metals, which may allow the construction of d–f heterometallic clusters and the investigation of their potential applications.

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Fig. 1: Synthesis of multimetallic bridged clusters.
Fig. 2: Molecular structures of 2, 3-U2Ni2Cl2, 4-U2Ni2 and 5-U2Ni3.
Fig. 3: Highest doubly occupied molecular orbital of 4-U2Ni2 and 5-U2Ni3.
Fig. 4: Electronic structure studies by SQUID magnetometry and UV−visible absorption spectroscopy.

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Data availability

Crystal data of 1, 2, 3-U2Ni2Cl2, 4-U2Ni2 and 5-U2Ni3 have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under reference numbers CCDC-1842367 (1), 1842368 (2), 1843093 (3-U2Ni2Cl2), 1843092 (4-U2Ni2) and 1842369 (5-U2Ni3). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre (www.ccdc.cam.ac.uk/data_request/cif). All other data supporting the findings of this study are available within the article and its Supplementary Information, or from the corresponding author upon reasonable request.

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Acknowledgements

This research was supported by the National Natural Science Foundation of China (grant no. 21772088), the Natural Science Foundation of Jiangsu Province (grant no. BK20170635), the Fundamental Research Funds for the Central Universities, the program of Jiangsu Specially-Appointed Professor and the Young Elite Scientist Sponsorship Program of the China Association of Science and Technology. The authors thank Y. Song (Nanjing University) and S. Jiang (Peking University) for useful discussion.

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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

    Genfeng Feng, Mingxing Zhang, Dong Shao, Xinyi Wang & Congqing Zhu

  2. State Key Laboratory of Radiation Medicine and Protection, School for Radiological and interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou, China

    Shuao Wang

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

    Laurent Maron

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Contributions

C.Z. conceived this project. G.F. performed the synthesis experiments. M.Z. solved all of the X-ray structures. D.S. performed the SQUID experiments. C.Z. and G.F. analysed the experimental data. L.M. conducted the theoretical computations and analysed the results. C.Z. and L.M. drafted the paper with support from G.F., X.W. and S.W. All the authors discussed the results and contributed to the preparation of the final manuscript.

Corresponding authors

Correspondence to Laurent Maron or Congqing Zhu.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

Experimental procedures; Supplementary figures; X-ray crystallographic analysis; theoretical calculations; Supplementary references

Crystallographic data

CIF for compound 1; CCDC reference: 1842367

Crystallographic data

CIF for compound 2; CCDC reference: 1842368

Crystallographic data

CIF for compound 3-U2Ni2Cl2; CCDC reference: 1843093

Crystallographic data

CIF for compound 4-U2Ni2; CCDC reference: 1843092

Crystallographic data

CIF for compound 5-U2Ni3; CCDC reference: 1842369

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Feng, G., Zhang, M., Shao, D. et al. Transition-metal-bridged bimetallic clusters with multiple uranium–metal bonds. Nature Chem 11, 248–253 (2019). https://doi.org/10.1038/s41557-018-0195-4

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