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Overcoming lability of extremely long alkane carbon–carbon bonds through dispersion forces

Nature volume 477, pages 308–311 (2011)Cite this article

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Abstract

Steric effects in chemistry are a consequence of the space required to accommodate the atoms and groups within a molecule, and are often thought to be dominated by repulsive forces arising from overlapping electron densities (Pauli repulsion). An appreciation of attractive interactions such as van der Waals forces (which include London dispersion forces) is necessary to understand chemical bonding and reactivity fully. This is evident from, for example, the strongly debated origin of the higher stability of branched alkanes relative to linear alkanes1,2 and the possibility of constructing hydrocarbons with extraordinarily long C–C single bonds through steric crowding3. Although empirical bond distance/bond strength relationships have been established for C–C bonds4 (longer C–C bonds have smaller bond dissociation energies), these have no present theoretical basis5. Nevertheless, these empirical considerations are fundamental to structural and energetic evaluations in chemistry6,7, as summarized by Pauling8 as early as 1960 and confirmed more recently4. Here we report the preparation of hydrocarbons with extremely long C–C bonds (up to 1.704 Å), the longest such bonds observed so far in alkanes. The prepared compounds are unexpectedly stable—noticeable decomposition occurs only above 200 °C. We prepared the alkanes by coupling nanometre-sized, diamond-like, highly rigid structures known as diamondoids9. The extraordinary stability of the coupling products is due to overall attractive dispersion interactions between the intramolecular H•••H contact surfaces, as is evident from density functional theory computations with10 and without inclusion of dispersion corrections.

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Figure 1: Hydrocarbons with exceptionally long C–C bonds.
Figure 2: Diamondoids and X-ray crystal structures of their coupling products with very long central C–C bonds.

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Acknowledgements

We thank S. Grimme for providing an implementation of his dispersion correction technique and for discussions. We are grateful for support from the Deutsche Forschungsgemeinschaft and the National Science Foundation of the USA, and in part from the Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering, under contract DE-AC02-76SF00515; the Ministry of Science and Education of Ukraine; and the Ukrainian State Basic Research Fund.

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Authors and Affiliations

  1. Institut für Organische Chemie der Justus-Liebig-Universität, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany ,

    Peter R. Schreiner, Heike Hausmann & Andrey A. Fokin

  2. Department of Organic Chemistry, Kiev Polytechnic Institute, 37 Pobeda Avenue, Kiev 03056, Ukraine,

    Lesya V. Chernish, Pavel A. Gunchenko, Evgeniya Yu. Tikhonchuk & Andrey A. Fokin

  3. Institut für Anorganische Chemie der Justus-Liebig-Universität, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany ,

    Michael Serafin & Sabine Schlecht

  4. Stanford University, Stanford Institute for Materials & Energy Science, 476 Lomita Mall, Stanford, California 94305, USA ,

    Jeremy E. P. Dahl & Robert M. K. Carlson

Authors
  1. Peter R. Schreiner
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Contributions

P.R.S. and A.A.F. formulated the initial working hypothesis and provided, analysed and interpreted all experimental data. L.V.C, P.A.G. and E.Yu.T. carried out the coupling experiments. H.H. recorded and analysed all NMR data. M.S. solved all X-ray structures. S.S. provided and interpreted the DSC and TGA analyses. J.E.P.D. and R.M.K.C. isolated and purified the diamondoids. The manuscript was written by P.R.S. and A.A.F.

Corresponding authors

Correspondence to Peter R. Schreiner or Andrey A. Fokin.

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The authors declare no competing financial interests.

Additional information

X-ray crystal structures have been deposited in the Cambridge Crystallographic Database under the deposition numbers CCDC 805315 (7•7), CCDC 806293 (6•8) and CCDC 806294 (7•8).

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Supplementary Information

This file contains Supplementary Figures 1-14 with legends, Supplementary Methods and Data, Supplementary Tables 1-3 and additional references. (PDF 5587 kb)

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Schreiner, P., Chernish, L., Gunchenko, P. et al. Overcoming lability of extremely long alkane carbon–carbon bonds through dispersion forces. Nature 477, 308–311 (2011). https://doi.org/10.1038/nature10367

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