The R 3O +·H + hydrogen bond: Toward a tetracoordinate oxadionium(2+) ion

Evgenii S. Stoyanov, Gorkem Gunbas, Nema Hafezi, Mark Mascal, Irini V. Stoyanova, Fook S. Tham, Christopher A. Reed

Research output: Contribution to journalArticle

30 Scopus citations

Abstract

Oxatriquinanes are tricyclic oxonium ions which are known to possess remarkable solvolytic stability compared to simple alkyl oxonium salts. Their rigid, hemispherical structure presents an oxygen at the apex of three fused five-membered rings. While trivalent oxygen species like these have been well described in the literature, the ability of oxygen to enter into a fourth covalent bonding relationship has been visited in theory and suggested by the outcome of certain reactions conducted in superacidic media, but has never been established by the characterization of a stable, persistent R 3OH 2+ or R 4O 2+ ion. In this study, the nucleophilicity of the oxatriquinane oxygen was evaluated first by a series of protonation studies using the Brønsted superacid H(CHB 11Cl 11) both in the solid state and in liquid HCl solution. The interaction of the oxatriquinane oxygen with a bridging carbocation was also examined. A strong case could be made for the occurrence of hydrogen bonding between H(CHB 11Cl 11) and oxatriquinane using IR spectroscopy. Under the most forcing protonation conditions, the oxatriquinane ring is cleaved to give a bridged, dicationic, protonated tetrahydrofuran-carbenium ion.

Original languageEnglish (US)
Pages (from-to)707-714
Number of pages8
JournalJournal of the American Chemical Society
Volume134
Issue number1
DOIs
StatePublished - Jan 11 2012

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

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    Stoyanov, E. S., Gunbas, G., Hafezi, N., Mascal, M., Stoyanova, I. V., Tham, F. S., & Reed, C. A. (2012). The R 3O +·H + hydrogen bond: Toward a tetracoordinate oxadionium(2+) ion. Journal of the American Chemical Society, 134(1), 707-714. https://doi.org/10.1021/ja209942s