Small-Molecule Catalysis of Heterobimetallic Groups 8 and 9 Transition Metal Complexes

Abstract

The unifying theme behind the chemistry described in this thesis is the desire to develop novel transition metal complexes for the catalytic transformation of exceptionally strong, and largely inert chemical bonds. Interest in the functionalization of these types of small molecules is driven mostly by applications found within industrially relevant catalysis, but also in part by concerns with environmental remediation. This introductory chapter aims to provide a glimpse into the motivations in studying transition metal complexes in this catalytic context and a brief sampling of the systems and chemistry relevant to the later chapters. In depth spectroscopic, structural, and theoretical studies on the nature of these complexes will be discussed, as well as the methodologies of their catalysis in the later chapters. The focus is the study of bimetallic systems in Chapter 2:) to leverage a direct Sn-Fe interaction to mediate the conversion of N2 to NH3 and examine the electronic effects the Sn bonding interaction has on the trans N2 ligand moiety, and Chapters 3 and 4:) to leverage Lewis acidic Ga–Rh and Ga–Co interactions for a new type of photoredox catalysts for the hydrodefluorination of aryl fluorides and trifluoroarenes, and to compare and contrast the reactivity and mechanistic differences between analogous photocatalysts with first and second row metals.