Reactivity of different forms of the µ-amido-µ-peroxo-bis[bis(ethylenediamine)cobalt(III)] complex: oxidation with tris(1,10-phenanthroline)-iron(III)

Abstract

The kinetics of oxidation of the µ-amido-µ-peroxo-bis[bis(ethylenediamine)cobalt(III)] complex with tris(1,10-phenanthroline)iron(III) have been studied, pH 0–2, with a view to obtaining further information regarding reactivities of the different forms of the µ-amido-µ-peroxo-complex. The unprotonated complex, B, is the only reactive form. At 25 °C and l= 0·245M(LiClO₄): k_B=(8·1 ± 0·8)× 10⁵| mol^–1 s^–1; ΔH_B‡=–1·1 ± 0·08 kcal mol^–1, and ΔS_B‡=–35·1 ± 0·85 cal K^–1 mol^–1. Possible structures for the protonated, BH, form of the complex are considered.