KINETICS AND MECHANISM OF EPOXIDATION OF CYCLOHEXENE AND CYCLOOCTENE WITH POTASSIUM HYDROGEN PERSULFATE CATALYZED BY AQUOETHYLENEDIAMINETETRAACETATORUTHENATE(III) COMPLEX ION IN WATER DIOXANE MEDIUM

The kinetics of oxygenation of [(EDTA)Ru(III)(H2O)]- to [(EDTA)Ru(V)(O)]- by KHSO5 was studied spectrophotometrically by following the appearance of characteristic peak of [(EDTA)Ru(V)(O)]- (EPSILON-393(max) = 8000) at a fixed pH of 6.0 and ionic strength 0.2 M (NaClO4). The time course of subsequent oxygen transfer from [(EDTA)Ru(V)(O)]- to cyclohexene and cyclooctene was investigated by following the decrease in the characteristic oxo peak at 393 nm as a function of substrate concentration and temperature (30-50-degrees-C) at a constant pH of 6 and ionic strength 0.2 M (NaClO4). Activation parameters for both the oxygenation of [(EDTA)Ru(III)(H2O)]- to [(EDTA)Ru(V)(O)]- and oxygen atom transfer from [(EDTA)Ru(V)(O)]- to cyclohexene and cyclooctene were determined and probable mechanisms for both reactions proposed.