RuIII(edta) mediated oxidation of azide in the presence of hydrogen peroxide. Azide versus peroxide activation†
Abstract
The [RuIII(edta)(H2O)]− (edta4− = ethylenediaminetetraacetate) complex catalyzes the oxidation of azide (N3−) with H2O2, mimicking the action of metallo-enzymes such as catalase and peroxidase in biochemistry. The kinetics of the catalytic oxidation process was studied by using stopped-flow and rapid-scan spectrophotometry as a function of [RuIII(edta)], [H2O2], [N3−] and pH. The catalytic activity of the different oxidizing species produced in the reaction of [RuIII(edta)(H2O)]− with H2O2 for the oxidation of azide was compared to the oxidation of coordinated azide in [RuIII(edta)N3]2− by H2O2. Detailed reaction mechanisms in agreement with the spectroscopic and kinetic data are presented for both reaction paths.