Kinetics and mechanism of the oxidation of alcohols by ruthenate and perruthenate ions

Abstract

In addition to being important synthetic reagents, ruthenate and perruthenate are of interest because they are representative of a number of high valent transition metal ions that can be used as oxidants in organic chemistry. In their reactions with alcohols both ions exhibit several striking similarities — concave Hammett plots, primary deuterium isotope effects, small enthalpies of activation, and large negative entropies of activation. The most likely explanation of the concave upward Hammett plots is the involvement of free radical-like transition states that could be formed by the decomposition of organometallic intermediates. Keywords: oxidation, ruthenate, perruthenate, alcohols, mandelic acid.