Addition of Methyl Radical to Substituted Alkenes: A Theoretical Study of the Reaction Mechanism

Ming Wah Wong, Addy Pross, Leo Radom

Research output: Contribution to journalArticlepeer-review

43 Scopus citations

Abstract

Ab initio calculations at the QCISD(T)/6–311G** level have been carried out to study the addition of the methyl radical to a series of substituted alkenes, and the results analyzed with the aid of the curve‐crossing model. It is found that (a) reaction exothermicity is the main factor that dominates reactivity, (b) polar contributions to the transition states are generally small and of minor energetic consequences, and (c) the general observation that π‐electron‐accepting substituents in the alkene enhance reactivity is a secondary correlation that is a consequence of the effect of these substituents on reaction exothermicity. There is no evidence for the prevalent view that the methyl radical is generally nucleophilic towards alkenes.

Original languageEnglish
Pages (from-to)415-425
Number of pages11
JournalIsrael Journal of Chemistry
Volume33
Issue number4
DOIs
StatePublished - 1 Jan 1993
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry (all)

Fingerprint

Dive into the research topics of 'Addition of Methyl Radical to Substituted Alkenes: A Theoretical Study of the Reaction Mechanism'. Together they form a unique fingerprint.

Cite this