Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

2013

Journal or Book Title

Journal of the American Chemical Society

Volume

135

Issue

24

First Page

9078

Last Page

9082

DOI

10.1021/ja403370k

Abstract

Photolysis of protonated phenylhydroxylamine was studied using product analysis, trapping experiments, and laser flash photolysis experiments (UV–vis and TR3 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.

Comments

Reprinted (adapted) with permission from J. Am. Chem. Soc., 2013, 135 (24), pp 9078–9082. Copyright 2013 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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