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Thorium(iv)–antimony complexes exhibiting single, double, and triple polar covalent metal–metal bonds

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Abstract

There is continued burgeoning interest in metal–metal multiple bonding to further our understanding of chemical bonding across the periodic table. However, although polar covalent metal–metal multiple bonding is well known for the d and p blocks, it is relatively underdeveloped for actinides. Homometallic examples are found in spectroscopic or fullerene-confined species, and heterometallic variants exhibiting a polar covalent σ bond supplemented by up to two dative π bonds are more prevalent. Hence, securing polar covalent actinide double and triple metal–metal bonds under normal experimental conditions has been a fundamental target. Here we exploit the protonolysis and dehydrocoupling chemistry of the parent dihydrogen-antimonide anion, to report one-, two- and three-fold thorium–antimony bonds, thus introducing polar covalent actinide–metal multiple bonding under normal experimental conditions between some of the heaviest ions in the periodic table with little or no bulky-substituent protection at the antimony centre. This provides fundamental insights into heavy element multiple bonding, in particular the tension between orbital-energy-driven and overlap-driven covalency for the actinides in a relativistic regime.

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Fig. 1: Synthesis of Th–Sb complexes 5–10, 18C6 = 18-crown-6 ether.
Fig. 2: Single-crystal X-ray diffraction solid-state structures of 5, 6, 7 and 8 at 150, 140, 100 and 120 K, respectively with displacement ellipsoids at 40% and selective labelling.
Fig. 3: Single-crystal X-ray diffraction solid-state structures of 9 and 10 at 100 and 105 K, respectively, with displacement ellipsoids at 40% and selective labelling.
Fig. 4: NLMOs for truncated 5′, 7 and truncated 8′ with non-Sb H atoms and weakly or non-coordinated {K(L)}+ (L = 18C6, 2.2.2-crypt) cations omitted.
Fig. 5: NLMOs for truncated 10′ with non-Si H atoms omitted.

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Data availability

The X-ray crystallographic coordinates for structures reported in this study have been deposited with the Cambridge Crystallographic Data Centre (CCDC), under deposition numbers CCDC 2285677 (5), 2285678 (6), 2285679 (7), 2285680 (8), 2285681 (9) and 2285682 (10). These data can be obtained free of charge from CCDC via www.ccdc.cam.ac.uk/data_request/cif. All other data are presented in the main text and the Supplementary Information, and are also available from the corresponding authors on reasonable request.

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Acknowledgements

We thank the Engineering and Physical Sciences Research Council (grants EP/T011289/1, EP/P001386/1, EP/M027015/1, and EP/W029057/1, S.T.L.), European Research Council (CoG612724, S.T.L.), Deutsche Forschungsgemeinschaft (HA 3466/11-1, C.v.H.), Philipps-Universität Marburg (K.D., C.v.H.) and the University of Manchester including computational resources and associated support services from the Computational Shared Facility (J.D., J.A.S., A.J.W., S.T.L.). The Alexander von Humboldt Foundation is thanked for a Friedrich Wilhelm Bessel Research Award (S.T.L.). We thank M. Jennings and A. Davies at the University of Manchester for CHN microanalyses.

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  1. Jingzhen Du

    Present address: College of Chemistry, Zhengzhou University, Zhengzhou, China

Authors and Affiliations

  1. Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Manchester, UK

    Jingzhen Du, John A. Seed, Ashley J. Wooles & Stephen T. Liddle

  2. Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Marburg, Germany

    Kevin Dollberg & Carsten von Hänisch

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Contributions

J.D. synthesized the thorium–antimony complexes and characterized them. K.D. prepared the antimony reagent. J.A.S. recorded the optical data and fitted them to the TD-DFT calculations. A.J.W. collected and refined the crystallographic data. S.T.L. conducted the quantum chemical calculations. C.v.H. and S.T.L. conceived the research idea, directed the research, analysed and interpreted all the data, and wrote the manuscript, with contributions from all the authors.

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Correspondence to Carsten von Hänisch or Stephen T. Liddle.

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Supplementary information

Supplementary Information

Crystallographic alerts and justifications, Supplementary Figs. 1–70 and Tables 1–10.

Supplementary Data 1

Cif data for 5 including fcf.

Supplementary Data 2

Cif data for 6 including fcf.

Supplementary Data 3

Cif data for 7 including fcf.

Supplementary Data 4

Cif data for 8 including fcf.

Supplementary Data 5

Cif data for 9 including fcf.

Supplementary Data 6

Cif data for 10 including fcf.

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Du, J., Dollberg, K., Seed, J.A. et al. Thorium(iv)–antimony complexes exhibiting single, double, and triple polar covalent metal–metal bonds. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01448-6

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