Comparison of the Addition of CH3∗ CH2OH∗, and CH2CN∗ Radicals to Substituted Alkenes: A Theoretical Study of the Reaction Mechanism

Ming Wah Wong, Addy Pross, Leo Radom

Research output: Contribution to journalArticlepeer-review

122 Scopus citations

Abstract

High-level ab initio calculations at the QCISD/6-311G∗∗ + ZPVE level have been carried out to study the addition reactions of CH3∗, CH2OH∗, and CH2CN∗ radicals to the substituted alkenes CH2=CHX (X = H, NH2, F, CI, CHO, and CN) and the results analyzed with the aid of the curve-crossing model. We find that the reactivity of CH3∗ is primarily governed by enthalpy effects, whereas both enthalpy and polar effects are important for the reactions of CH2OH∗ and CH2CN∗ There is no general barrier height-enthalpy correlation for the latter two radicals because of the presence in some cases of polar effects that stabilize the transition states without a corresponding stabilization of the products. The polar effects are not sufficient, however, to significantly shift the location of the transition states, so a general structure-enthalpy correlation is observed.

Original languageEnglish
Pages (from-to)6284-6292
Number of pages9
JournalJournal of the American Chemical Society
Volume116
Issue number14
DOIs
StatePublished - 1 Jul 1994

ASJC Scopus subject areas

  • Catalysis
  • Chemistry (all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint

Dive into the research topics of 'Comparison of the Addition of CH3∗ CH2OH∗, and CH2CN∗ Radicals to Substituted Alkenes: A Theoretical Study of the Reaction Mechanism'. Together they form a unique fingerprint.

Cite this