Date of Award
Doctor of Philosophy in Clinical-Bioanalytical Chemistry
The chemical oxidation of ferrocene and related derivatives (RFc) via organic peroxides solvated in acetonitrile was studied spectrophotometrically by varying concentration and temperature to determine kinetics and activation parameters. The reaction rate of ferrocene with dibenzoyl peroxide depends strongly on whether electron withdrawing or donating substituents are present. Products were analyzed and the effect of different solvents on reactivity were studied. The rate law was first order in both oxidant and reductant, and steric and solvent effects are consistent with outer sphere electron transfer (ET) as the rate-controlling step. B3YLP calculations were conducted to determine reorganization energies using Marcus theory and to examine molecular geometry and steric considerations.
Halstead, Jos M., "Oxidation of Ferrocene Derivatives with Dibenzoyl Peroxide and Meta-Chloroperoxybenzoic Acid" (2018). ETD Archive. 1108.