Extreme oxatriquinanes and a record C-O bond length

Gorkem Gunbas, Nema Hafezi, William L. Sheppard, Marilyn M. Olmstead, Irini V. Stoyanova, Fook S. Tham, Matthew P. Meyer, Mark Mascal

Research output: Contribution to journalArticle

24 Citations (Scopus)

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.

Original languageEnglish (US)
Pages (from-to)1018-1023
Number of pages6
JournalNature Chemistry
Volume4
Issue number12
DOIs
StatePublished - Dec 2012

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Bond length
Ions
Elongation
Ethers
Substitution reactions
Salts
Derivatives
X rays
hydronium ion

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Gunbas, G., Hafezi, N., Sheppard, W. L., Olmstead, M. M., Stoyanova, I. V., Tham, F. S., ... Mascal, M. (2012). Extreme oxatriquinanes and a record C-O bond length. Nature Chemistry, 4(12), 1018-1023. https://doi.org/10.1038/nchem.1502

Extreme oxatriquinanes and a record C-O bond length. / Gunbas, Gorkem; Hafezi, Nema; Sheppard, William L.; Olmstead, Marilyn M.; Stoyanova, Irini V.; Tham, Fook S.; Meyer, Matthew P.; Mascal, Mark.

In: Nature Chemistry, Vol. 4, No. 12, 12.2012, p. 1018-1023.

Research output: Contribution to journalArticle

Gunbas, G, Hafezi, N, Sheppard, WL, Olmstead, MM, Stoyanova, IV, Tham, FS, Meyer, MP & Mascal, M 2012, 'Extreme oxatriquinanes and a record C-O bond length', Nature Chemistry, vol. 4, no. 12, pp. 1018-1023. https://doi.org/10.1038/nchem.1502
Gunbas G, Hafezi N, Sheppard WL, Olmstead MM, Stoyanova IV, Tham FS et al. Extreme oxatriquinanes and a record C-O bond length. Nature Chemistry. 2012 Dec;4(12):1018-1023. https://doi.org/10.1038/nchem.1502
Gunbas, Gorkem ; Hafezi, Nema ; Sheppard, William L. ; Olmstead, Marilyn M. ; Stoyanova, Irini V. ; Tham, Fook S. ; Meyer, Matthew P. ; Mascal, Mark. / Extreme oxatriquinanes and a record C-O bond length. In: Nature Chemistry. 2012 ; Vol. 4, No. 12. pp. 1018-1023.
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