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- Title
Solvent effect is not significant for the speed of a radical clock.
- Authors
Yao Fu; Rui-Qiong Li; Lei Liu; Qing-Xiang Guo
- Abstract
The UQCISD(T)/6-31g(d)//UB3LYP/16- 31g(d) method and PCM solvation model were used to study the solvent effects on radical clock reactions. The solvents included cyclohexane benzene tetrahydrofuran methylene chloride acetone methanol acetonitrile, dimethylsulfoxide nitromethane and water. We found very small solvent effects on the rearrangement activation free energy of cyclobutylmethyl and 1-hexen-6-yl radicals. Therefore, it is valid to use a calibrated radical clock in an unclear reaction medium because the speed of the radical clock should not change significantly by the solvent effect. In addition, we separated the solvent effects on radical rearrangement into three components, electrostatic, cavitation and dispersion/repulsion. We discussed the contribution of each component in detail.
- Subjects
CYCLOHEXANE; ALICYCLIC compounds; ELECTROSTATICS; BUTYL methyl ether; CAVITATION; HYDRODYNAMICS
- Publication
Research on Chemical Intermediates, 2004, Vol 30, Issue 3, p279
- ISSN
0922-6168
- Publication type
Article
- DOI
10.1163/156856704323034012