Direct Detection and Reactivity of the Short-Lived Phenyloxenium Ion

dc.contributor.author Hanway, Patrick
dc.contributor.author Xue, Jiadan
dc.contributor.author Winter, Arthur
dc.contributor.author Bhattacharjee, Ujjal
dc.contributor.author Milot, Maeia
dc.contributor.author Ruixue, Zhu
dc.contributor.author Phillips, David
dc.contributor.author Winter, Arthur
dc.contributor.department Chemistry
dc.date 2018-02-17T06:48:14.000
dc.date.accessioned 2020-06-30T01:17:53Z
dc.date.available 2020-06-30T01:17:53Z
dc.date.copyright Tue Jan 01 00:00:00 UTC 2013
dc.date.issued 2013-01-01
dc.description.abstract <p>Photolysis of protonated phenylhydroxylamine was studied using product analysis, trapping experiments, and laser flash photolysis experiments (UV–vis and TR<sup>3</sup> detection) ranging from the femtosecond to the microsecond time scale. We find that the excited state of the photoprecursor is followed by two species: a longer-lived transient (150 ns) that we assign to the phenoxy radical and a shorter-lived (3–20 ns) transient that we assign to the singlet phenyloxenium ion. Product studies from photolysis of this precursor show rearranged protonated <em>o</em>-/<em>p</em>-aminophenols and solvent water adducts (catechol, hydroquinone) and ammonium ion. The former products can be largely ascribed to radical recombination or ion recombination, while the latter are ascribed to solvent water addition to the phenyloxenium ion. The phenyloxenium ion is apparently too short-lived under these conditions to be trapped by external nucleophiles other than solvent, giving only trace amounts of <em>o</em>-/<em>p</em>-chloro adducts upon addition of chloride trap. Product studies upon thermolysis of this precursor give the same products as those generated from photolysis, with the difference being that the <em>ortho</em> adducts (<em>o</em>-aminophenol, hydroquinone) are formed in a higher ratio in comparison to the photolysis products.</p>
dc.description.comments <p>Reprinted (adapted) with permission from J. Am. Chem. Soc., 2013, 135 (24), pp 9078–9082. Copyright 2013 American Chemical Society.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/chem_pubs/140/
dc.identifier.articleid 1166
dc.identifier.contextkey 7886751
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath chem_pubs/140
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/14574
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/140/0-2013_Winter_DirectDetection_License.pdf|||Fri Jan 14 20:11:43 UTC 2022
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/140/2013_Winter_DirectDetection.pdf|||Fri Jan 14 20:11:45 UTC 2022
dc.source.uri 10.1021/ja403370k
dc.subject.disciplines Materials Chemistry
dc.subject.disciplines Other Chemistry
dc.subject.disciplines Physical Chemistry
dc.title Direct Detection and Reactivity of the Short-Lived Phenyloxenium Ion
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication a2121da6-c591-494f-b9a9-595265e46ff9
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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