Mechanistic Insights into the Role of Sulfur Ligation in the Oxidative Reactivity of Non-heme High-valent Iron Complexes

Abstract

This thesis investigates the generation, characterization, and reactivity of various sulfur-ligated high-valent non-heme iron intermediates. Specifically, it focuses on the chemistry of non-heme iron(IV)-oxo, iron(IV)-tosylimido, and iron(III)-alkylperoxo systems. Chapter III demonstrates the significant impact of substituting a sulfur ligand for an N-CH3 group on the reactivity of the iron(IV)-oxo species. Chapter IV details the creation of a sulfur-ligated iron(IV)-tosylimido complex and compares its properties with those of the iron(IV)-oxo analogue. Chapter V presents the generation of a sulfur-ligated iron(III)-alkylperoxo species and introduces a novel mechanism for its reaction with aldehydes.