On the determination and use of reduction potentials of short-lived radicals. A review

A method, the "competition method", for the determination of reduction pote ntials and estimation of standard potentials for short-lived radicals is re viewed. Applications of the reduction potentials of radicals as arguments f or reaction mechanisms are presented for the Grignard reaction, the photore duction of ketones with alcohols, and the SRN1 reaction. Reductions induced by hydroxide ions are discussed in more detail, and the classic reaction b etween nitrosobenzene and hydroxide ion in aqueous solution is used as an e xample of such a reaction. A nucleophilic attack by hydroxide ion rather th an an electron transfer initiates the reduction sequence. A review with 26 references.