Taming the Highly Reactive Oxonium Ion

Haley, Michael M.

doi:10.1002/anie.200805417

Cited by 10 publications

(2 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently, we described the preparation of oxatriquinane 2 , 19 an oxonium analogue of the previously reported azatriquinane 3 . 20 The fused, tricyclic framework of 2 was found to impart remarkable stability compared to other cyclic oxonium species, 21 such that salts of 2 could be recrystallized from boiling water or even chromatographed.…”

Section: Introductionmentioning

confidence: 99%

The R₃O⁺···H⁺ Hydrogen Bond: Toward a Tetracoordinate Oxadionium(2+) Ion

et al. 2011

View full text Add to dashboard Cite

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 established by the characterization of a stable, persistent R3OH++ or R4O++ ion. In this study, the nucleophilicity of the oxatriquinane oxygen was evaluated first by a series of protonation studies using the Brønsted superacid H(CHB11Cl11) 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(CHB11Cl11) 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.

show abstract

Section: Introductionmentioning

confidence: 99%

The R₃O⁺···H⁺ Hydrogen Bond: Toward a Tetracoordinate Oxadionium(2+) Ion

et al. 2011

View full text Add to dashboard Cite

show abstract

“…In these molecules the O + ion is stabilized by fusing it inside a tricyclic condensed ring. [2][3][4] The lack of reactivity of these species against nucleophilic attack is associated with the ring strain, revealing the potential of embedding oxonium ions in ring frameworks for their stability. Subsequently, an oxatriquinane with a hydroxyl group in the a-position to oxygen was found to possess the longest C-O bond length reported to date (1.658 Å).…”

Section: Introductionmentioning

confidence: 99%