Oxidation of substrates tethered to N-donor ligands for modeling non-heme diiron enzyme active sites

摘要

Chapter 1. Modeling Carboxylate-Rich Diiron Sites of Dioxygen-Dependent Non-Heme Enzymes Carboxylate-bridged diiron centers are employed in a variety of biological systems to activate dioxygen for substrate oxidation, and small molecule models have been synthesized to mimic this chemistry outside of the natural systems. In this introductory chapter a brief overview of terphenyl-based carboxylate systems is given and progress toward achieving structural, spectroscopic, and functional models of the protein active sites is reviewed. Chapter 2. Synthesis and Reactivity of Carboxylate-Bridged Diiron(II) Complexes with Primary Alkyl Amine Ligands The synthesis and crystallographic characterization of a series of diiron(II) complexes with sterically hindered terphenyl carboxylate ligands and alkyl amine donors are presented. The compounds ... , where ... 2,6-di(p-tolyl)benzoate, and [...] (L= NH₂(CH₂)₃SMe (4); NH₂(CH₂)₃CCH (5)), where ... is 2,6-di(3,5- dimethylphenyl)benzoate, were prepared as small molecule mimics of the catalytic sites of carboxylate-bridged non-heme diiron enzymes.