Theoretical studies of isomerization reactions of 2-pentoxy radical and its derivatives including the unsaturated alkoxy radicals

Ching Yeh Lin, Jia Jen Ho

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Abstract

This paper deals with the calculation of isomerization reactions of 2-pentoxy radical and its derivatives (including unsaturated alkoxy radicals) by density functional theory. The results indicate that the process via six-membered ring TS calculated at the B3LYP/6-311++G** level for 2-pentoxy had the lowest energy barrier, 8.63 kcal/mol. However, in the unsaturated derivatives, the energy barriers very much depend on the double bond position in the molecule, and that may alter the isomerization processes. The substitution effect on the isomerization barrier was as well investigated. The calculated lowest energy barrier of the substituted compound of 2-pentoxy was 3.77 kcal/mol of 5,5-dimethyl-2-pentoxy radical. We found that the relative stability of the isomerization products was one of the important factors concerning the barrier. Usually, the isomerization takes place via a six-membered TS to have almost free ring-strain energy. Nevertheless, our calculation shows that it is possible to find the substituted unsaturated alkoxy derivatives to proceed via a smaller ring transition structure (five-membered, instead of six-membered) to have lower energy barrier.

Original languageEnglish
Pages (from-to)4137-4144
Number of pages8
JournalJournal of Physical Chemistry A
Volume106
Issue number16
DOIs
Publication statusPublished - 2002 Apr 25

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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