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The isomerization of methoxy radical: Intramolecular hydrogen atom transfer mediated through acid catalysis

Journal of the American Chemical Society, ISSN: 0002-7863, Vol: 133, Issue: 7, Page: 2013-2015
2011
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Article Description

The catalytic ability of water, formic acid, and sulfuric acid to facilitate the isomerization of the CHO radical to CHOH has been studied. It is shown that the activation energies for isomerization are 30.2, 25.7, 4.2, and 2.3 kcal mol, respectively, when the reaction is carried out in isolation and with water, formic acid, or sulfuric acid as a catalyst. The formation of a doubly hydrogen bonded transition state is central to lowering the activation energy and facilitating the intramolecular hydrogen atom transfer that is required for isomerization. The changes in the rate constant for the CHO-to-CHOH isomerization with acid catalysis have also been calculated at 298 K. The largest enhancement in the rate, by over 12 orders of magnitude, is with sulfuric acid. The results of the present study demonstrate the feasibility of acid catalysis of a gas-phase radical isomerization reaction that would otherwise be forbidden. © 2011 American Chemical Society.

Bibliographic Details

Buszek, Robert J; Sinha, Amitabha; Francisco, Joseph S

American Chemical Society (ACS)

Chemical Engineering; Chemistry; Biochemistry, Genetics and Molecular Biology

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