Syntheses, characterization, and computational study of AsF5 adducts with ketones

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dc.contributor.authorStuart, Daniel
dc.contributor.authorWetmore, Stacey D.
dc.contributor.authorGerken, Michael
dc.date.accessioned2021-07-29T19:58:01Z
dc.date.available2021-07-29T19:58:01Z
dc.date.issued2019
dc.descriptionAccepted author manuscripten_US
dc.description.abstractLewis acid-base adducts between AsF5 and the ketones, acetone, cyclopentanone, and adamantanone, were synthesized from SO2 and CH2Cl2 solutions. These adducts, which contain O---As pnictogen bonding interactions, were found to be stable in solutions at room temperature. Raman and NMR spectroscopy of the solid adducts showed a characteristic decrease in the C=O stretching frequency, as well as dramatic deshielding of the 13C resonance of the carbonyl group upon adduct formation. Fluorine-19 NMR spectroscopy showed the two fluorine environments of the O–AsF5 moiety. Optimization of the gas-phase geometry using DFT calculations yielded geometries with essentially planar CC=OAs moieties. NBO analyses of the adducts and the free ketones show the polarization of the C=O bond upon adduct formation. The lowering of the LUMO energies upon adduct formation is more dramatic than what was found for protonation of ketones and reflects the substantially enhanced electrophilicity of the adducted ketones.en_US
dc.description.peer-reviewYesen_US
dc.identifier.citationStuart, D., Wetmore, S. D., & Gerken, M. (2019). Syntheses, characterization, and computational study of AsF5 adducts with ketones. Journal of Fluorine Chemistry, 221, 9-16. https://doi.org/10.1016/j.jfluchem.2019.02.011en_US
dc.identifier.urihttps://hdl.handle.net/10133/5975
dc.language.isoen_USen_US
dc.publisherElsevieren_US
dc.publisher.departmentDepartment of Chemistry and Biochemistryen_US
dc.publisher.facultyArts and Scienceen_US
dc.publisher.institutionUniversity of Lethbridgeen_US
dc.publisher.institutionCanadian Centre for Research in Advanced Fluorine Technologiesen_US
dc.publisher.urlhttps://doi.org/10.1016/j.jfluchem.2019.02.011en_US
dc.subjectLewis-acid-base adductsen_US
dc.subjectPnictogen bondingen_US
dc.subjectDFT calculationsen_US
dc.subjectAdducts
dc.subject.lcshLewis acids
dc.subject.lcshKetones
dc.subject.lcshRaman spectroscopy
dc.titleSyntheses, characterization, and computational study of AsF5 adducts with ketonesen_US
dc.typeArticleen_US
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