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Issue 32, 2015
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Direct observation of vinyl hydroperoxide

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Abstract

Many alkyl-substituted Criegee intermediates are predicted to undergo an intramolecular 1,4-hydrogen transfer to form isomeric vinyl hydroperoxide species (C[double bond, length as m-dash]COOH moiety), which break apart to release OH and vinoxy radicals. We report direct detection of stabilized vinyl hydroperoxides formed via carboxylic acid-catalyzed tautomerization of Criegee intermediates. A doubly hydrogen-bonded interaction between the Criegee intermediate and carboxylic acid facilitates efficient hydrogen transfer through a double hydrogen shift. Deuteration of formic or acetic acid permits migration of a D atom to yield partially deuterated vinyl hydroperoxides, which are distinguished from the CH3CHOO, (CH3)2COO, and CH3CH2CHOO Criegee intermediates by mass. Using 10.5 eV photoionization, three prototypical vinyl hydroperoxides, CH2[double bond, length as m-dash]CHOOD, CH2[double bond, length as m-dash]C(CH3)OOD, and CH3CH[double bond, length as m-dash]CHOOD, are detected directly. Complementary electronic structure calculations reveal several reaction pathways, including the barrierless acid-catalyzed tautomerization reaction predicted previously and a barrierless addition reaction that yields hydroperoxy alkyl formate.

Graphical abstract: Direct observation of vinyl hydroperoxide

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Publication details

The article was received on 20 May 2015, accepted on 08 Jul 2015 and first published on 22 Jul 2015


Article type: Communication
DOI: 10.1039/C5CP02917A
Citation: Phys. Chem. Chem. Phys., 2015,17, 20490-20494
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    Direct observation of vinyl hydroperoxide

    F. Liu, Y. Fang, M. Kumar, W. H. Thompson and M. I. Lester, Phys. Chem. Chem. Phys., 2015, 17, 20490
    DOI: 10.1039/C5CP02917A

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