AM1 studies on alkyl and allyl radical additions to methyl-substituted ethenes and on the β-bond scissions of the radicals formed

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The addition reactions of alkyl and allyl radicals in terminal (t) and non-terminal (n) positions to unsubstituted and methyl-substituted ethenes (propene, 2-methylpropene, 2-methyl-2-butene and 2,3-dimethyl-2-butene) were studied at the semiempirical quantum-chemical level by means of Austin Model 1 (AM1) with half-electron (HE) and unrestricted Hartree-Fock (UHF) approximations. The transition states on the potential energy surfaces were determined with full geometrical optimization by means of the McIver-Komornicki method. The calculated enthalpies of activation (ΔH‡) were found to be greater for the allyl radical additions than for the methyl radical additions in both t and n positions. The ΔH‡ values were greater in the additions of both methyl and allyl radicals to the n position. The Evans-Polanyi correlations between the calculated ΔH° and ΔrH° were justified and the validity of the Hammond postulate was indicated.

Original languageEnglish
Pages (from-to)135-146
Number of pages12
JournalJournal of Molecular Structure: THEOCHEM
Volume277
Issue numberC
DOIs
Publication statusPublished - Dec 10 1992

    Fingerprint

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this