Oxidation kinetics of ferrocene derivatives with dibenzoyl peroxide

Publication date: Available online 27 October 2018Source: Journal of Organometallic ChemistryAuthor(s): Joshua M. Halstead, Refaat Abu-Saleh, Steven M. Schildcrout, John MasnoviAbstractChemical oxidation of ferrocene and related derivatives by dibenzoyl peroxide in acetonitrile solution produces ferrocenium and benzoic acid after acidification. The rate law is first order in oxidant and in reductant. Steric effects and activation parameters are consistent with a rate-controlling outer-sphere single-electron transfer (ET) step, and reorganization energies are obtained using Marcus theory with B3LYP calculations. Energetics, optimized structures, and solvent effects indicate that rate is affected more by anion than cation solvation and that oxidation of decamethylferrocene by 3-chloroperoxybenzoic acid does not occur by ET.Graphical abstract

Source: Journal of Organometallic Chemistry - October 27, 2018 Category: Chemistry Source Type: research