Green oxidation catalysis with iron-TAML/peroxide: Novel applications in microbial deactivation, kinetic and mechanistic studies

Chapter 1. Fe-TAML catalysts are efficient activators especially of peroxides, and of dioxygen to some degree. An introduction to the Fe-TAML activators is provided here. The treatment covers the various demonstrated applications and includes a discussion of the kinetic and reactivity studies performed to date. A short introduction is given to each of the following thesis chapters.; Chapter 2. Better lines of defense against biological warfare and terrorism (BWT) agents are crucially needed. One imperative calls for decontamination technologies that rapidly deactivate BWT pathogens in diverse scenarios while being nontoxic, user-friendly, materials compatible, environmentally benign, and economically viable. A relatively innocuous sporicidal system is described that employs green oxidation catalysis using Fe-TAML activators of peroxide.; Chapter 3. As explained in this chapter, Fe-TAML catalysts have been used in micromolar concentrations with H2O2 to deactivate T2 phage viruses as surrogates for viral contaminants in water. A 105-fold reduction in T2 phage population was achieved in 5 minutes. The combined effectiveness of the Fe-TAML catalysts in deactivation of bacterial spores and viruses implies that there is considerable potential that the Fe-TAML/peroxide system might provide a superior method for water purification to any currently available.; Chapter 4. It is expected that Fe-TAML activators will often be used in real world applications in combination with surfactants. The kinetics and mechanism of oxidation of two organic dyes, Orange II and Sudan III, by Fe-TAML activated H2O2 and tert -butyl hydroperoxide (tBuOOH) were studied at the aqueous/micellar interphase.; Chapter 5. Very recently, an oxo-bridged dimer (Fe IV-O-FeIV), a FeV(O), and a Fe IV(O) species have been characterized from three separate studies. In this work, the reactivities of these high valent iron-oxo species have been investigated. These high valent iron-oxo species were reacted with a variety of substrates, such as triphenylphosphine, thioanisole and para-substituted thioanisoles, different alkanes, and other reductants in aqueous and non-aqueous solvents. The oxo-bridged dimer and the iron(IV)-oxo monomer were generated at room temperature in water with their reactivity studies being carried out in water, while the iron(V)-oxo species was produced and its reactivity studies carried out in acetonitrile at -40°C. Detailed kinetic studies have been performed to determine the equilibrium parameters and rate constants involved in the oxidation of different substrates by these high valent species.; Chapter 6. Selective oxidation of organic sulfides to sulfoxides is an important synthetic challenge. Several transition metal based catalysts have been developed to carry out sulfide oxidation reactions, using H2O2 as a "green" oxidant. Unlike most catalytic systems, Fe-TAML catalysts have been found to be very efficient in activating H 2O2 in water, at room temperature. In this work, the Fe-TAML/peroxide system has been used to perform selective oxidation of various aliphatic and aromatic sulfides to corresponding sulfoxides or sulfones by varying the reaction conditions, with the reactions being carried out under homogeneous reaction conditions. In a further study enacted with a view to facilitating easy product separation and reuse of the catalysts, a Fe-TAML activator was supported onto Merrifield's resin using ionic interactions. (Abstract shortened by UMI.)...