Influence of medium on the kinetics of oxidation of iron(II) ion with t-butyl hydroperoxide

• Published in: Chemical papers 2006-08, Vol.60 (4), p.253-267
• Main Authors: Mihaljević, B., Ražem, D.
• Format: Article
• Language: English
• ISSN: 1336-9075; 1336-9075
• DOI: 10.2478/s11696-006-0045-5

The oxidation of iron(II) with tert-butyl hydroperoxide was investigated in the absence of oxygen in water, methanol, and the dichloromethane—methanol solvent mixture (φr = 2:1). The oxidation rate depends on solvent polarity; measured in the presence of SCN− at constant 0.8 mmol dm−3 HCl, the rate constant increases with the polarity decrease passing from water and methanol to the dichloromethane—methanol solvent mixture. Further, in non-aqueous solutions at this acid concentration the rate constant was higher than the rate constant in the presence of Cl− only. The oxidation rate measured in the [FeCl]2+ complex in dichloromethane—methanol was slow in acidic medium and increased by decreasing the acid concentration. Approaching the physiological pH conditions the rate constant attained the value of an order of magnitude of 103 dm3 mol−1 s−1, while very little alteration of stoichiometry of the oxidation reaction was observed. The rate constant measured in the presence of Cl− strongly depends on electrolyte concentration at concentrations less than 0.5 mmol dm−3 HCl, both in MeOH and the solvent mixture. Based on these results, a possible mechanism of the influence of solvent, acidity, and ligand type on the rate constant is discussed. We assume that the oxidation proceeds by an inner-sphere mechanism considering that the breakdown of the successor inner-sphere complex forming reactive alkoxyl radicals is probably the rate-limiting step.