Metal-catalysed organic photoreactions. Evidence for the long-range electron-transfer mechanism in the uranyl- or iron(III)-catalysed photoreactions of olefins

Abstract

A scheme involving interligand electron transfer from the electron-donating ligand (OH^– or Cl^–) to molecular oxygenn through the metal ion and olefin molecule is proposed for the metal-catalysed photo-oxidation of olefins. The scheme is verified for the uranyl-catalysed photochemical formation of bromohydrins from olefins and various polyhalogenated compounds by correlation of the reactivities and product ratios with the half-wave reduction potentials of the polyhalogenated compounds.