✦ LIBER ✦
Cyclic vs. acyclic allylic hydrogen abstraction: An entropy motivated process?
✍ Scribed by Gadi Rothenberg; Yoel Sasson
- Book ID
- 104208541
- Publisher
- Elsevier Science
- Year
- 1998
- Tongue
- French
- Weight
- 261 KB
- Volume
- 54
- Category
- Article
- ISSN
- 0040-4020
No coin nor oath required. For personal study only.
✦ Synopsis
Optimized geometries for the reactants, products, and transition structures of cyclic and acyclic allylic hydrogen abstractions by tert-butoxy radicals were obtained by semiempirical methods. In the four model cases studied the transition structures were all early and linear, with large imaginary frequencies, around 2000 cm -*. Enthalpic effects, rather than entropic ones, are deemed as responsible for the "cyclic activation" of allylic hydrogens towards free-radicals.