**The presence of a negative partial charge on the benzylic carbon atom in the transition state** __(1)__ can be deduced from the experimentally determinable Hammett Ο± values. Alkyl radicals R^Λ^ are accordingly seen to develop nucleophilic properties during addition to olefins. equation image
Polar Effects in Halogen Abstraction Reactions of Alkyl Radicals
β Scribed by Giese, Bernd ;Hartung, Jens
- Publisher
- Wiley (John Wiley & Sons)
- Year
- 1992
- Tongue
- English
- Weight
- 322 KB
- Volume
- 125
- Category
- Article
- ISSN
- 0009-2940
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π SIMILAR VOLUMES
Methyl radicals substituted by one ester or nitrile group are on the borderline between nucleophilic and electrophilic behavior. In addition reactions of these borderline radicals to styrenes, polar effects of both, electron-withdrawing and electron-donating substituents at the alkeae, increase the
Rate constants (k) of radical addition reactions between 15 carbon-and sulfur-centered radicals and 15 vinyl-type alkenes were collected from the literature. Three descriptor variables {a polar (Hammett) sigma scale [s(H)] and two radical sigma scales as defined by Creary and co-workers [s Γ (C)] an