Electronic Activation and Tuning of Redox-Active Ligand Orbitals

Abstract

This dissertation focuses upon the synthesis, characterization and reactivity of thiolate-ligated α-(imino)-N-heterocycle complexes. Chapter 1 provides an introduction to cysteinate ligated metalloenzymes and synthetic model systems containing redox-active ligands. Chapter 2 discusses the synthesis and characterization of three thiolate ligated iron (II) α-(imino)-N-heterocycle complexes displaying unique spectroscopic features. Chapter 3 highlights the unique activation of the α-(imino)-N-heterocycles due to the coordinated thiolate through the role of electrochemistry, sulfur K-edge X-ray absorption spectroscopy and computations. Chapter 4 exhibits the role of the geometry around the metal center and the effect of the thiolate through a cobalt, manganese and thioether derivatives. Chapter 5 presents a unique nucleophilic attack of a thiolate forming a thiazolidine ring structure. The results described will highlight the ability to fine tune these redox-active orbitals which have a large role in multi-electron base metal catalysis.