Biomimetic metal-mediated reactivity

Control of catalytic oxidation reactions is difficult to achieve because of the formation of undesirable by-products and degradation of the catalyst, hence the development of efficient, cheap and sustainable region- and stereoselective oxidation catalysts is a highly desirable goal. In Nature transition metals in the active site of enzymes create a unique chemical environment making activation of dioxygen for the use of selective catalytic substrate oxidation possible. A fundamental chemical understanding of the short-lived metal-based oxidants of the key steps in the oxidation processes is important for the development of new greener oxidation catalysts. Molecular iron model complexes mimicking this bioreactivity have shown to be a central approach in the strategy of catalyst design.

The work presented in this Ph.D. thesis focuses on the potency and use of an iron catalyst based on a non-heme ligand scaffold. The reactivity of the iron catalyst is evaluated in combination with different oxidants in both organic and aqueous solutions. The ligand design differs distinctly compared to the three last three decades of reports on this class of iron-based oxidation catalysts, which is reflected in different reactivity patterns for this system. The choice of oxidant can guide the catalyst on either a selective or a promiscuous oxidation pathway giving the iron catalyst a remarkable diversity in its reactivity.

Dissertation: http://hdl.handle.net/11370/f7a4991a-84cc-40a1-9647-f7184ea0242e