Investigation on the efficiency of recognition-driven C(sp3)-H oxidation by non-heme FeIV(O) complexes. A quantitative study on the impact of substrate proximity on the reactivity, selectivity and rebound efficiency of oxidation reaction

In the present thesis, the results obtained from the investigation of substrate proximity and orientation effects in the oxidation reactions of C(sp3)-H bonds catalyzed by non-heme FeIV(O) complexes will be presented. Chapter 1 is a general introduction about chemistry of non-heme FeIV(O) complexes in biological and biomimetic environments. Their reactivity in C(sp3)-H oxidation is discussed in terms of initial hydrogen atom transfer (HAT) and subsequent oxygen rebound. These paragraphs are followed by a brief description of how supramolecular chemistry offers a powerful method to replicate enzyme-like properties in synthetic catalysts. General introduction is followed by chapter 2, where the aim of the research work investigated in this thesis is presented. In chapter 3, the role of substrate recognition in the C(sp3)-H oxidation catalysis of a biomimetic non-heme FeIV(O) complex is discussed in terms of induced proximity and orientation effects. We compared the reactivity of two different complexes which differ in their capacity of binding or not the target substrate in the second coordination sphere In chapter 4, the effect of changing the orientation of the receptor in a supramolecular non-heme FeIV(O) catalyst is discussed. Specifically, we compared the reactivity and selectivity profiles of the oxidation of a target substrate with two different complexes which only differ in the orientation of supramolecular receptor binding group.