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Hydrocarbon analogues of boron clusters — planarity, aromaticity and antiaromaticity

Nature Materials volume 2, pages 827–833 (2003)Cite this article

Abstract

An interesting feature of elemental boron and boron compounds is the occurrence of highly symmetric icosahedral clusters. The rich chemistry of boron is also dominated by three-dimensional cage structures. Despite its proximity to carbon in the periodic table, elemental boron clusters have been scarcely studied experimentally and their structures and chemical bonding have not been fully elucidated. Here we report experimental and theoretical evidence that small boron clusters prefer planar structures and exhibit aromaticity and antiaromaticity according to the Hückel rules, akin to planar hydrocarbons. Aromatic boron clusters possess more circular shapes whereas antiaromatic boron clusters are elongated, analogous to structural distortions of antiaromatic hydrocarbons. The planar boron clusters are thus the only series of molecules other than the hydrocarbons to exhibit size-dependent aromatic and antiaromatic behaviour and represent a new dimension of boron chemistry. The stable aromatic boron clusters may exhibit similar chemistries to that of benzene, such as forming sandwich-type metal compounds.

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Figure 1: Photoelectron spectra of Bx− (x = 10–15).
Figure 2: The low-lying structures of B12− and B13− and their neutrals.
Figure 3: The low-lying structures of B10−, B11−, B14− and B15−, and their neutrals.
Figure 4: Comparison of the occupied π molecular orbitals (MOs) of benzene with those of boron clusters.
Figure 5: Analogy of the aromaticity and antiaromaticity between boron clusters and hydrocarbons.

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Acknowledgements

This work was supported by the US National Science Foundation (DMR-0095828) and partly by the Petroleum Research Fund administered by the American Chemical Society and performed at the EMSL, a national scientific user facility sponsored by Department of Energy's (DOE) Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory, operated for DOE by Battelle. All the calculations were performed using supercomputers at EMSL Molecular Science Computing Facility.

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Authors and Affiliations

  1. Department of Physics, Washington State University, 2710 University Drive, Richland, 99352, Washington, USA

    Hua-Jin Zhai, Boggavarapu Kiran & Lai-Sheng Wang

  2. W. R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, 99352, Washington, USA

    Hua-Jin Zhai, Boggavarapu Kiran, Jun Li & Lai-Sheng Wang

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Zhai, HJ., Kiran, B., Li, J. et al. Hydrocarbon analogues of boron clusters — planarity, aromaticity and antiaromaticity. Nature Mater 2, 827–833 (2003). https://doi.org/10.1038/nmat1012

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