Collect. Czech. Chem. Commun. 2000, 65, 829-843

On the Determination and Use of Reduction Potentials of Short-Lived Radicals. A Review

Henning Lund*, Karen Skov, Steen Uttrup Pedersen, Torben Lund and Kim Daasbjerg

Department of Organic Chemistry, University of Aarhus, DK-8000 Aarhus C, Denmark


A method, the "competition method", for the determination of reduction potentials and estimation of standard potentials for short-lived radicals is reviewed. Applications of the reduction potentials of radicals as arguments for reaction mechanisms are presented for the Grignard reaction, the photoreduction of ketones with alcohols, and the SRN1 reaction. Reductions induced by hydroxide ions are discussed in more detail, and the classic reaction between nitrosobenzene and hydroxide ion in aqueous solution is used as an example of such a reaction. A nucleophilic attack by hydroxide ion rather than an electron transfer initiates the reduction sequence. A review with 26 references.

Keywords: Redox potentials; Reductions; Reaction mechanism; Grignard reaction; Ketones; Photoreductions.

References: 34 live references.