DFT Study on the pH Dependence of the Reactivity of Ferrate(VI)

Density-functional-theory (DFT) study on methanol oxidation by ferrate (FeO 4 2- ) in water is reviewed in this chapter. The oxidizing power of three species, non-protonated, monoprotonated, and diprotonated ferrates was evaluated by using the B3LYP-D method. The oxidizing power increases in the order non-protonated ferrate < monoprotonated ferrate < diprotonated ferrate. The reaction pathway is initiated by C–H bond activation, which is the rate-determining in the overall reaction. Kinetic aspects of the reaction are analyzed from calculated energy profiles and experimentally known p K a values. The pH dependence of this reaction in water is explained well in terms of a multi-oxidant scheme.