Iron coordination chemistry of nitrogen,diazene,hydrazin,and ammonia : Investigating the mechanism of nitrogen reduction to ammonia

The coordination chemistry of iron with N2 is becoming increasingly important as chemists try to find alternative routes to the production of ammonia. Current biological and industrial processes use iron to catalyze the formation of ammonia from N2; however, huge amounts of energy are required for this conversion. Understanding how dinitrogen and other intermediates of dinitrogen reduction interact with iron could lead to energy efficient processes for the production of ammonia.;This dissertation explores the synthesis and reactivity of an iron dinitrogen complex that reacts with acid to produce ammonia at room temperature and pressure. This dissertation also explores the progress toward determining the mechanism of this reaction in hopes of improving the yields of ammonia.;Chapter I describes both the biological nitrogen fixation process and the industrial production of ammonia and provides an in-depth look at progress toward an alternative route to ammonia using iron complexes described in the literature thus far.;Chapter II details the synthesis, characterization, and reactivity of dihydrogen and dinitrogen complexes of iron. These complexes are precursors to the active ammonia producing complex and are among a handful of dihydrogen and dinitrogen complexes that have been structurally characterized. Chapter III explores the synthesis and stability of Fe(DMeOPrPE)2N 2. This complex produces ammonia and hydrazine upon protonation with a strong acid. Optimizing the yield of ammonia from this protonation is also described.;Chapter IV discusses the synthesis and reactivity of several complexes of iron containing intermediates relevant to dinitrogen reduction, including diazene (N2H2), hydrazine (N2H4), and ammonia. By studying these intermediates, a mechanism of ammonia formation from the protonation of Fe(DMeOPrPE)2N2 is proposed that may also provide insights into the mechanism of nitrogenase. Chapter V provides a summary of this research.;This dissertation includes previously published and unpublished co-authored material.