Kinetics of the Acid Hydrolysis of Carboxylatopentammineruthenium(III) Complexes

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The kinetics of the hydrolysis of pentammineruthenium(III) complexes containing carboxylates and α-substituted acetates (glycolate and glycinate) have been studied. The experiments were carried out in a solution of [H+]=0.025–0.1M, at 40–70°C. For each complex, the rate law was found to be: rate=[complex](kH2O+kH[H+]). The kH2O and kH values for the formato, acetato, propionato, isobutyrato, glycolato, and glycinato complexes are, respectively (at μ=0.10, 59–61°C): kH2O, 5.37×10−5, 11.8×10−5, 14×10−5, 13.7×10−5, 5.7×10−5, and 6.75×10−5sec−1; kH, 3.3×10−3, 2.3×10−3, 2.5×10−3, 1.7×10−3, 0.75×10−3, and 3.1×10−3M−1sec−1. The mechanisms of acid hydrolysis are discussed for the two reaction paths.
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