Pearce, Adam2020-05-042020-05-042020-01https://hdl.handle.net/11299/213094University of Minnesota Ph.D. dissertation. January 2020. Major: Chemistry. Advisor: Ian Tonks. 1 computer file (PDF); 3 xxv, 276 pages.The utilization of redox non-innocent ligands and substrates can grant access to new modes of reactivity in organometallic chemistry, allowing for the development of new sustainable methods with earth-abundant catalysts. Through the use of valence tautomerism in nitrogenous ligands and substrates (azides, azobenzene, isodiazenes, etc.), new organometallic reactions have been developed—the atom economical synthesis of important organic molecules such as pyrroles, pyrazoles and imines through titanium redox catalysis and an exploration of the valence tautomerism of an iridium(III)-hydrazido(2-) capable of oxidative addition.encatalysisiridiumorganometallicpyrazoleredoxtitaniumThesis or Dissertation