| Abstract: | Reactions of oxygenated cobalt(II) complexes. IX. Oxidative properties of tetrakis(ethylenediamine)-μ-peroxo-μ-hydroxo-dicobalt(III) 1 VIII s. 1]. (en)2Co(O2, OH)Co(en)2]3+ ( a ) reacts with I? in acidic aqueous solution according to: CoIII(O2, OH)CoIII + 21? + 5H+ ? 2CoIII + 3H2O + I2. Using I? in excess first order rate constants are obtained which, to a first approximation, are independent of I?]. Comparison with kinetic data of deoxygenation of (en)2Co(O2, OH)Co(en)2]3+ under analogous conditions suggests that both reactions have the same rate determining step. The singly bridged species (en)2(H2O)CoO2Co(H2O) (en)2]4+ is shown to be the reactive intermediate in the iodide oxidation (Schema 2). |
