KINETICS AND MECHANISM OF OSMIUM TETROXIDE CATALYZED OXIDATION OF ACETONE AND ETHYL METHYL KETONE BY ALKALINE HEXACYANOFERRATE(3) ION

The studies in the kinetics of the osmium tetroxide catalyzed oxidation of acetone and ethyl methyl ketone by aqueous alkaline potassium hexacyanoferrate(III) were made at four temperatures to investigate the way osmium tetroxide participates as catalyst in the oxidation of ketones. The data suggest that the oxidation of these ketones proceeds via the formation of an activated complex between the enolate and osmium tetroxide which rapidly decomposes followed by a fast reaction between the reduced osmium species and ferricyanide. The product study has made it possible to give the intermediates and the reactions which occur. © 1969, American Chemical Society. All rights reserved.