Free-radical reactions depend on a reagent having a (relatively) weak bond, allowing it to homolyse to form radicals (often with heat or light). Reagents without such a weak bond would likely proceed via a different mechanism. An example of an addition reaction involving aryl radicals is the Meerwein arylation.
A radical substitution reaction is a reaction which occurs by a free radical mechanism and results in the substitution of one or more of the atoms or groups present in the substrate by different atoms or groups. The initiation step in a radical chain reaction is the step in which a free radical is first produced.
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