Solid-state structure of a protonated ketones and aldehydes

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dc.contributor.authorStuart, Daniel
dc.contributor.authorWetmore, Stacey D.
dc.contributor.authorGerken, Michael
dc.date.accessioned2021-07-14T16:19:44Z
dc.date.available2021-07-14T16:19:44Z
dc.date.issued2017
dc.descriptionAccepted author manuscripten_US
dc.description.abstractProtonated carbonyl compounds have been invoked as intermediates in many acid-catalyzed organic reactions. To gain key structural and electronic data about such intermediates, oxonium salts derived from five representative examples of ketones and aldehydes are synthesized in the solid state, and characterized by X-ray crystallography and Raman spectroscopy for the first time. DFT calculations were carried out on the cations in the gas phase. Whereas an equimolar reaction of the carbonyl compounds, acetone, cyclopentanone, adamantanone, and acetaldehyde, with SbF5 in anhydrous HF yielded mononuclear oxonium cations, the same stoichiometry in a reaction with benzaldehyde resulted in formation of a hemiprotonated, hydrogen-bridged dimeric cation. Hemiprotonated acetaldehyde was obtained when a 2:1 ratio of aldehyde and SbF5 was used. Experimental and NBO analyses quantify the significant increase in electrophilicity of the oxonium cations compared to that of the parent ketones/aldehydes.en_US
dc.description.peer-reviewYesen_US
dc.identifier.citationStuart, D., Wetmore, S. D., & Gerken, M. (2017). Solid-state structure of protonated ketones and aldehydes. Angewandte Chemie International Edition, 56(51), 16380-16384. https://doi.org/10.1002/anie.201710263en_US
dc.identifier.urihttps://hdl.handle.net/10133/5958
dc.language.isoen_USen_US
dc.publisherWileyen_US
dc.publisher.departmentDepartment of Chemistry and Biochemistryen_US
dc.publisher.facultyArts and Scienceen_US
dc.publisher.institutionUniversity of Lethbridgeen_US
dc.publisher.urlhttps://doi.org/10.1002/anie.201710263en_US
dc.subjectDensity functional calculationsen_US
dc.subjectOxonium cationen_US
dc.subjectReactive intermediatesen_US
dc.subjectSuperacidic systemsen_US
dc.subjectX-ray diffractionen_US
dc.subject.lcshDensity functionals
dc.subject.lcshOxonium ions
dc.subject.lcshIntermediates (Chemistry)
dc.subject.lcshKetones
dc.subject.lcshAldehydes
dc.subject.lcshCations
dc.titleSolid-state structure of a protonated ketones and aldehydesen_US
dc.typeArticleen_US
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