Small Molecule Activation Studies Involving Thiolate-Ligated Manganese(II) Complexes and Biologically-Relevant Oxidants

Abstract

This dissertation focuses upon the synthesis, characterization, and reactivity of thiolate-ligated manganese complexes. Chapter 1 provides a brief introduction to the importance of manganese ions in biology, as well as the unique properties promoted by thiolate ligands. Chapter 2 discusses the synthesis and characterization of a library of structurally-analogous manganese(II) complexes used for further studies. Chapters 3-5 discuss the reactivity of the complexes discussed in Chapter 2 with various biologically-relevant oxidants, such as dioxygen, superoxide, and peroxides. Finally, Chapter 6 discusses the synthesis, characterization, and reactivity of model complexes for the manganese lipoxygenase metalloenzyme family. The results described throughout this dissertation provide many rare and unique insights into the role played by manganese in biology, as well as how various reaction intermediate species formed from manganese complexes may have relevance to reactions catalyzed in biology.