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Insights from domain-averaged Fermi hole (DAFH) analysis and multicenter bond indices into the nature of Be(0) bonding

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Summary

The nature of the bonding interactions in the recently synthesized first stable neutral complex of so-called zero-valent beryllium (i.e. formally Be(0)) is investigated using the analysis of domain-averaged Fermi holes (DAFHs) and of multicenter bond indices. It is shown that both of these types of analysis, which have previously proved useful for various molecules with nontrivial bonding patterns, basically corroborate the appealing model suggested in the original study to explain the stability of the complex (except for a more realistic specification of the actual valence state of the Be atom). Nevertheless, as well as confirming the anticipated dominance of three-center two-electron π bonding in the central C−Be−C fragment, reinforced by the existence of two donor-acceptor Be−C σ bonds, a more detailed scrutiny of the multicenter bond indices also reveals somewhat unexpected features which suggest also the existence of delocalized 3c-4e σ bonding in the C−Be−C skeleton.

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Scheme 1
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Notes

  1. For the sake of mathematical rigor it is also possible to reformulate the whole approach in terms of density matrices instead of densities [45]; this choice of formulation has no practical impact on the actual application of the DAFH analysis to a particular system.

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Acknowledgments

The authors thank Prof. István Mayer (Hungarian Academy of Sciences, Budapest) for stimulating discussions and critical comments.

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  1. Institute of Chemical Process Fundamentals, Czech Academy of Sciences v.v.i., Rozvojová 135, 165 02, Prague 6 - Suchdol 2, Czech Republic

    Robert Ponec

  2. Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK

    David L. Cooper

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Ponec, R., Cooper, D.L. Insights from domain-averaged Fermi hole (DAFH) analysis and multicenter bond indices into the nature of Be(0) bonding. Struct Chem 28, 1033–1043 (2017). https://doi.org/10.1007/s11224-017-0914-2

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