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Carbon-free sandwich compounds based on arsenic and antimony with icosahedral metal cores

Nature Synthesis volume 2, pages 423–429 (2023)Cite this article

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Abstract

Traditionally, a metallocene complex comprises a metal centre sandwiched between two aromatic organic ligands and such complexes have been extensively investigated. Carbon-free analogues of metallocene with homoleptic As5 or Sb5 ligands, however, have remained experimentally elusive, especially analogues of higher nuclearity. Here we report the synthesis and characterization of sandwich-type clusters [Pn@M12Pn10(Pn5)2]4–/5– (Pn = As, Sb; M = Co, Fe), where the endohedral icosahedral cluster [Pn@M12] can be regarded as a spherical-like three-dimensional coordination centre surrounded by a Pn10 ring and two Pn5 pentagonal caps. Quantum chemical calculations reveal that the [Pn@M12] has orbitals that mimic 1S, 1P and 1D electronic shells, which can interact with the outer (Pn5)2 ring layer. These interactions occur because the frontier orbitals are dominated by the (n − 1)d block orbitals of the metal atoms. The π1-As5 orbitals interact with 1S and part of the 1P shell of the central core, while the π2- and π3-As5 orbitals interact with the symmetry-allowed part of the 1P and 1D shells. The characteristics of this orbital interaction are analogous to those of mononuclear metallocenes.

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Fig. 1: Selected examples of known and predicted sandwich complexes with cyclopentadienyl or cyclo-P5, cyclo-As5 and cyclo-Sb5 ligands.
Fig. 2: Molecular structures of the cluster anions [Pn@M12Pn10(Pn5)2]5– (Pn = As, Sb; M = Co, Fe) and their selected fragments.
Fig. 3: Selected orbitals revealing the bonding interaction in [As@Co12@As10(As5)2]4–.

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Data availability

Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2204629 (1′), 2204630 (2′), 2204596 (3′). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the Article and its Supplementary Information.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (92161102, 21971118 and 22003048) and the Natural Science Foundation of Tianjin City (numbers 21JCZXJC00140 and 20JCYBJC01560) to Z.-M.S. Z.-M.S. thanks the 111 project (B18030) from China (MOE). A.M.C. thanks ANID for regular grant 1221676.

Author information

Author notes

  1. These authors contributed equally: Xu-Hui Yue, Wei-Xing Chen.

Authors and Affiliations

  1. State Key Laboratory of Elemento-organic Chemistry, Tianjin Key Lab of Rare Earth Materials and Applications, School of Material Science and Engineering, Nankai University, Tianjin, China

    Xu-Hui Yue, Wei-Xing Chen & Zhong-Ming Sun

  2. MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi’an Jiaotong University, Xi’an, China

    Tao Yang

  3. Facultad de Ingeniería, Arquitectura y Diseño, Universidad San Sebastián, Santiago, Chile

    Alvaro Muñoz-Castro

  4. Donostia International Physics Center (DIPC), Donostia, Spain

    Gernot Frenking

  5. Fachbereich Chemie, Philipps-Universität Marburg, Marburg, Germany

    Gernot Frenking

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Contributions

Z.-M.S. conceived and directed the research. X.-H.Y. synthesized compounds 1′ and 2′. W.-X.C. synthesized compound 3′. A.M.-C. and T.Y. performed the computational studies. X.-H.Y. and W.-X.C. performed the single-crystal X-ray diffraction, EDX and ESI-MS, and analysed the data. All authors co-wrote the manuscript.

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Correspondence to Zhong-Ming Sun.

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Nature Synthesis thanks Giovanni Maestri and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary handling editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–19, Discussion and Tables 1–7.

Supplementary Data 1

Crystallographic data for complex 1′ (CCDC 2204629).

Supplementary Data 2

Crystallographic Data for complex 2′ (CCDC 2204630).

Supplementary Data 3

Crystallographic data for complex 3′ (CCDC 2204596).

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Yue, XH., Chen, WX., Yang, T. et al. Carbon-free sandwich compounds based on arsenic and antimony with icosahedral metal cores. Nat. Synth 2, 423–429 (2023). https://doi.org/10.1038/s44160-023-00247-0

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