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Extreme oxatriquinanes and a record C–O bond length

Nature Chemistry volume 4, pages 1018–1023 (2012)Cite this article

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Abstract

Oxatriquinanes are fused, tricyclic oxonium ions that are known to have exceptional stability compared to simple alkyl oxonium salts. C–O bonds in ethers are generally ∼1.43 Å in length, but oxatriquinane has been found to have C–O bond lengths of 1.54 Å. A search of the Cambridge Structural Database turned up no bona fide C–O bond length exceeding this value. Computational modelling of oxatriquinane alongside other alkyl oxonium ions indicated that the electronic consequences of molecular strain were primarily responsible for the observed bond elongation. We also show that substitution of the oxatriquinane ring system with alkyl groups of increasing steric demand pushes the C–O bond to unheard of distances, culminating in a tert-butyl derivative at a predicted 1.60 Å. Chemical synthesis and an X-ray crystallographic study of these compounds validated the results of the modelling work and, finally, an extraordinary 1.622 Å C–O bond was observed in 1,4,7-tri-tert-butyloxatriquinane.

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Figure 1: Bond length, angle and dihedral distortion energies for diethyl ether (MP2/6-31 + G**).
Figure 2: Trends in C–O distances versus bond attributes.
Figure 3: Synthesis of substituted oxatriquinanes 15 and 16.
Figure 4: Deuterium exchange in 15 in D3COD solution.
Figure 5: X-ray crystal structure of tri-tert-butyloxatriquinane 16 and its [CHB11Cl11]− counterion.

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Acknowledgements

This work was supported financially by the National Science Foundation (grants CHE-0957798 to M.M. and CHE-1058483 to M.P.M.). G.G. thanks the Turkish Higher Education Council for a studentship.

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Authors and Affiliations

  1. Department of Chemistry, University of California Davis, 1 Shields Avenue, Davis, 95616, California, USA

    Gorkem Gunbas, Nema Hafezi, William L. Sheppard, Marilyn M. Olmstead & Mark Mascal

  2. Department of Chemisty, University of California Riverside, 900 University Avenue, Riverside, 92521, California, USA

    Irini V. Stoyanova & Fook S. Tham

  3. Department of Chemistry and Biochemistry, University of California Merced, 5200 North Lake Road, Merced, 95343, California, USA

    Matthew P. Meyer

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Contributions

G.G. performed synthetic, computational and crystallographic work. N.H. and W.L.S. performed synthetic work. M.M.O. provided assistance with crystallographic work. I.V.S. obtained crystals of 16. F.S.T. performed the crystallographic work on 16. M.P.M. performed computational work and interpreted computational results. M.M. supervised the project, composed the manuscript, and performed database and computational work.

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Correspondence to Mark Mascal.

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Supplementary information

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Supplementary information (PDF 2721 kb)

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Crystallographic data for compound 13 (CIF 29 kb)

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Crystallographic data for compound 14 (CIF 16 kb)

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Crystallographic data for compound 15 (CIF 11 kb)

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Crystallographic data for compound 16 (CIF 51 kb)

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Gunbas, G., Hafezi, N., Sheppard, W. et al. Extreme oxatriquinanes and a record C–O bond length. Nature Chem 4, 1018–1023 (2012). https://doi.org/10.1038/nchem.1502

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