Abstract
The equilibria and kinetics of formation of catecholato(2–)iron(III) have been studied over the pH range 1·00–2·00 in aqueous media with the stopped-flow technique. At 25·0 °C and ionic strength 1·0M(NaClO4), the equilibrium constantKe for chelate-complex formation (i) is (4·35 ± 0·10)× l0–2 mol l–1 and ε[Fe(cat)+]=(1·25 ± 0·05)× 103l mol–1 at 700 nm. From the hydrogen-ion dependence of the reaction rate it can be shown that complex Fe3++ H2cat ⇌[Fe(cat)]++ 2H+(i), formation occurs between [FeOH]2+ ion and catechol with a rate constant k=(3·1 ± 0·2)× 103 l mol–1 s–1; estimated activation data are ΔH= 9·6 ± 1·0 kcal mol–1 and ΔS=–11·1 ± 3·0 cal K–1 mol–1. The experimental data are consistent with the accepted ld mechanism for ligand substitution.

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