Collect. Czech. Chem. Commun. 1988, 53, 3138-3148

Homogeneous catalysis of manganese(II) in acid bromate oxidation of olefinic acids

Ch. Sanjeeva Reddy

Department of Chemistry, Kakatiya University, Warangal 506 009, India


Manganese(II)-catalysed acid bromate oxidation of acrylic trans-crotonic and trans-cinnamic acids, in the presence of mercury(II), a bromide ion scavenger, exhibits first order in concentration of bromate, and reaches an upper limit with increase in substrate as well as catalyst concentration. Oxidation rate increases with acidity and is not altered when deuterium replaces either α or β proton of the olefinic acid. The catalytic effect of Mn(II) is displayed by its complex forming ability and the proposed mechanism assumes the oxidation of the formed Mn(II)-substrate π complex to Mn(III)-substrate π complex by acid bromate which further converts to products. The formation of a π complex between Mn(II) and the olefinic bond of the substrate is assumed for the first time.