Role of Steric Effects on Rates of Hydrogen Atom Transfer ReactionsClick to copy article linkArticle link copied!
- Yi SunYi SunYusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Rd, Cambridge CB21EW, EnglandMore by Yi Sun
- Fengjiao LiuFengjiao LiuCollege of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620, ChinaMore by Fengjiao Liu
- Jacob N. SandersJacob N. SandersDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United StatesMore by Jacob N. Sanders
- K. N. Houk*K. N. Houk*Email: [email protected]Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United StatesMore by K. N. Houk
Abstract

The influence of steric effects on the rates of hydrogen atom transfer (HAT) reactions between oxyradicals and alkanes is explored computationally. Quantum chemical density functional theory computations of transition states show that activation barriers and reaction enthalpies are both influenced by bulky substituents on the radical but very little by substituents on the alkane. The activation barriers remain roughly correlated with reaction enthalpies via the Evans–Polanyi relationship even when steric repulsion effects become important, although dispersion effects sometimes stabilize transition states. By making comparisons to previously developed Evans–Polanyi and modified Roberts–Steel relationships, we find that HAT reactions between bulky molecules remain well-described by these relationships.
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