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Article: Direct Detection and Reactivity of the Short-Lived Phenyloxenium Ion

TitleDirect Detection and Reactivity of the Short-Lived Phenyloxenium Ion
Authors
Issue Date2013
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal of the American Chemical Society, 2013, v. 135 n. 24, p. 9078-9082 How to Cite?
AbstractPhotolysis of protonated phenylhydroxylamine was studied using product analysis, trapping experiments, and laser flash photolysis experiments (UV-vis and TR(3) 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 o-/p-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 o-/p-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 ortho adducts (o-aminophenol, hydroquinone) are formed in a higher ratio in comparison to the photolysis products.
Persistent Identifierhttp://hdl.handle.net/10722/188228
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorHanway, PJ-
dc.contributor.authorXue, J-
dc.contributor.authorBhattacharjee, U-
dc.contributor.authorMilot, MJ-
dc.contributor.authorRuixue, Z-
dc.contributor.authorPhillips, DL-
dc.contributor.authorWinter, AH-
dc.date.accessioned2013-08-23T03:23:35Z-
dc.date.available2013-08-23T03:23:35Z-
dc.date.issued2013-
dc.identifier.citationJournal of the American Chemical Society, 2013, v. 135 n. 24, p. 9078-9082-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/188228-
dc.description.abstractPhotolysis of protonated phenylhydroxylamine was studied using product analysis, trapping experiments, and laser flash photolysis experiments (UV-vis and TR(3) 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 o-/p-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 o-/p-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 ortho adducts (o-aminophenol, hydroquinone) are formed in a higher ratio in comparison to the photolysis products.-
dc.languageeng-
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titleDirect Detection and Reactivity of the Short-Lived Phenyloxenium Ionen_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL: phillips@hku.hk-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ja403370k-
dc.identifier.pmid23713909-
dc.identifier.hkuros220088-
dc.identifier.volume135-
dc.identifier.issue24-
dc.identifier.spage9078-
dc.identifier.epage9082-
dc.identifier.isiWOS:000320899200047-
dc.publisher.placeUnited States-

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