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Dihydrogen contacts in alkanes are subtle but not faint

Nature Chemistry volume 3, pages 323–330 (2011)Cite this article

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Abstract

Alkane molecules are held together in the crystal state by purportedly weak homonuclear R–H···H–R dihydrogen interactions. In an apparent contradiction, the high melting points and vaporization enthalpies of polyhedranes in condensed phases require quite strong intermolecular interactions. Two questions arise: ‘How strong can a weak C–H···H–C bond be?’ and ‘How do the size and topology of the carbon skeleton affect these bonding interactions?’ A systematic computational study of intermolecular interactions in dimers of n-alkanes and polyhedranes, such as tetrahedrane, cubane, octahedrane or dodecahedrane, showed that attractive C–H···H–C interactions are stronger than usually thought. We identified factors that account for the strength of these interactions, including the tertiary nature of the carbon atoms and their low pyramidality. An alkane with a bowl shape was designed in the search for stronger dihydrogen intermolecular bonding, and a dissociation energy as high as 12 kJ mol−1 is predicted by our calculations.

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Figure 1: Size and polarizability effects on the intermolecular interactions of alkanes.
Figure 2: Size and pyramidality effects on the intermolecular interactions between polyhedranes.
Figure 3: Optimized geometries, shortest H···H contacts and BCPs in dimers of methane and polyhedranes.
Figure 4: H···H contacts in a dimer of a C20H30 buckybowlane.

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Acknowledgements

This work was supported by the Ministerio de Investigación, Ciencia e Innovación (MICINN, project CTQ2008-06670-C02-01-BQU), Generalitat de Catalunya (grants 2009SGR-1459 and XRQTC) and the Israel Science Foundation (ISF Grant 53/09). Allocation of computer time at the Centre de Supercomputació de Catalunya is acknowledged. The authors thank A. Lledós, R. Hoffmann, S. Olivella, P. Alemany, E. Ruiz and H. Rzepa for discussions and suggestions.

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Authors and Affiliations

  1. Departament de Química Inorgànica and Institut de Química Teòrica i Computacional, Universitat de Barcelona, Martí i Franquès 1-11, Barcelona, 08028, Spain

    Jorge Echeverría, Gabriel Aullón & Santiago Alvarez

  2. Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Jerusalem, 91904, Israel

    David Danovich & Sason Shaik

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  1. Jorge Echeverría
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Contributions

J.E. carried out literature searches of related computational and experimental work, performed geometry optimizations and electron-density analysis of the dimers of open-chain alkanes, small polyhedranes and the buckybowlane, and participated in the preparation of graphic material for the manuscript. G.A. performed the geometry optimizations and electron-density analyses of the dimers of large polyhedranes. D.D. carried out benchmark calculations to help select the most adequate computational methodology. S.S. designed the benchmark and exploratory calculations. S.A. conceived the project, helped design the computational goals and strategies and wrote the manuscript. All authors actively participated in the discussion of the results and in the design of new computational experiments, and made contributions to the manuscript.

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Correspondence to Sason Shaik or Santiago Alvarez.

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Echeverría, J., Aullón, G., Danovich, D. et al. Dihydrogen contacts in alkanes are subtle but not faint. Nature Chem 3, 323–330 (2011). https://doi.org/10.1038/nchem.1004

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