Abstract
The absolute rate constants for the addition of alkyl radicals to acrylonitrile and methyl acrylate are determined by evaluating the ratio of ligand-transfer oxidation and addition to the double bond. Secondary alkyl radi c ̵ als appear to be more reactive than primary alkyl radicals, despite the less favourable energetics. The classical selectivity : reactivity relationship is reversed owing to the nucleophilic character of the alkyl radicals.
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