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Free Radicals
Definition: Any chemical species with
one or more unpaired electrons
Nature of Free Radicals
Geometry
Rationalization to account for
racemization in radical reactions
Evidence in favor of the “pyramidal” radical
More evidence in favor of the “pyramidal” radical?
Stability of Free Radicals
Stabilities of Substituted Benzyl Radicals
Substituted Benzyl radicals
Steric effects
Generation of Free Radicals
 Thermolysis
 Photolysis
Generation of Free Radicals
Redox reactions
Characteristics of Radical
Reactions
 Most radical reactions occur readily in the gas phase
 Radical reactions generally are not influenced by solvent
polarity
 Radical reactions generally are not influenced by acid or
base catalysis
 Unlike cations or anions, radicals generally are not
influenced by electron-donating or electron-withdrawing
substituents
 Radical reactions are often preceded by an induction
period during which time they are subject to inhibition
 Radical reactions are frequently chain reactions
 Radical reactions generally are not accompanied by
skeletal rearrangements
A Typical Radical Reaction
Overall reaction
A Typical Radical Reaction: Mechanism

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radicals.ppt