Solvent effect is not significant for the speed of a radical clock

Solvent effect is not significant for the speed of a radical clock The UQCISD(T)/6-31g(d)//UB3LYP/6-31g(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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Solvent effect is not significant for the speed of a radical clock

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Publisher
Brill Academic Publishers
Copyright
Copyright © 2004 by VSP
Subject
Chemistry; Inorganic Chemistry; Physical Chemistry; Catalysis
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1163/156856704323034012
Publisher site
See Article on Publisher Site

Abstract

The UQCISD(T)/6-31g(d)//UB3LYP/6-31g(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.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Apr 1, 2004

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