Kinetics of oxidation of a 2-aminomethylpyridinechromium(III) complex by periodate

The oxidation kinetics of the 2-aminomethylpyridineCr^III complex with periodate in aqueous solution were studied and found to obey the rate law:Rate = [Cr^III]_T [IO₄ ^-]{k¹K² + k₂ K₁ K₃/[H⁺]}/{1+K₁/[H⁺] + k₂[IO₄ ^-]+K₁K₃/[H⁺][IO₄ ^-]} where K ₁, K ₂ and K ₃ are the deprotonation of [Cr(L)₂(H₂O)]³⁺ and pre-equilibrium formation constants for [(L)₂—Cr—OIO₃]²⁺ and [(L)₂—Cr—OH—OIO₃]⁺ precursor complexes respectively. An inner-sphere mechanism was proposed. The effect of Cu²⁺ on the oxidation rate was studied over the (1.0–9.0) × 10⁻⁵ mol dm⁻³ range. The reaction rate was found to be inversely proportional to the Cu²⁺ concentration over the range studied. This revised version was published online in June 2006 with corrections to the Cover Date.