Direct observation of vinyl hydroperoxide

Literature Information

Publication Date 2015-07-22
DOI 10.1039/C5CP02917A
Impact Factor 3.676
Authors

Fang Liu, Yi Fang, Manoj Kumar, Ward H. Thompson, Marsha I. Lester


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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 (CCOOH 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, CH2CHOOD, CH2C(CH3)OOD, and CH3CHCHOOD, 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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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