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The rational design of helium bonds

Nature Chemistry volume 2, pages 390–393 (2010)Cite this article

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An Addendum to this article was published on 20 June 2014

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Abstract

The chemistry of helium has hitherto been confined to experimental and theoretical analysis of small molecules containing three to five atoms in the gas phase. Here a new suggestion is made for compounds of helium deriving from a recent proposal that five-coordinate carbon might be captured as a frozen SN2 transition state. A series of logical steps, originally discussed as postings and comments to two blogs, led to the outcome described here of a central hypervalent atom bound on one face by a small cyclic carbon ligand, with the other free face having an interaction to a helium atom with the topological properties of a charge-shift rather than a covalent bond. Although high-level theory predicts these helium bonds to be quite short with relatively high stretching frequencies, the kinetic barriers to the loss of helium are predicted to be small, and are not increased by the strategy of having bulky substituents on the ring ligand.

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Figure 1: A screenshot of an interactive table that compiles calculated properties for molecular compounds of helium.
Figure 2: Form (eigenvectors) of the calculated normal transition state mode (green arrows) at the B2GP-PLYP/TZVPP level for the dissociation/combination of He for two systems.

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Change history

  • 20 June 2014

    The interactive version of the table shown in Fig. 1 of this Article is now additionally available at http://dx.doi.org/10.6084/m9.figshare.1009575. The online versions of the Article have been amended accordingly.

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  1. Department of Chemistry, Imperial College London, South Kensington Campus, Exhibition Road, London, SW7 2AZ

    Henry S. Rzepa

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Correspondence to Henry S. Rzepa.

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Rzepa, H. The rational design of helium bonds. Nature Chem 2, 390–393 (2010). https://doi.org/10.1038/nchem.596

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