Expanding f element utility: cordination chemistry, electronic structure, alkyl–alkyl cross–coupling catalysis, and C–H activation

Abstract

As the ever–increasing energy demands continue to increase for modern 21st century society, many industrial processes continue to use precious metal–based systems. The mining of these precious metals, primarily due to their dwindling concentration in the Earth’s crust, contributes heavily to greenhouse gas production and the warming of the planet. A major pursuit in modern chemistry aims at replacing the precious metals used in industrial settings with more earth abundant metals, as they are inexpensive and pose a minimal threat towards climate change. One class of Earth abundant metals that have been of considerable interest are the f elements, composed of the rare earth metals and the actinides. Specifically, the rare earth metals have found a wide range of applications in fields like quantum computing, electronic device manufacturing, medical instrumentations, and data storage. While they have been explored in mediating chemical processes, they are vastly underutilized primarily due to their lack of readily accessible redox chemistry. This dissertation highlights the rare earth metals in two distinct fields. First, the elucidation of their electronic structure in heterobimetallic complexes and the coordination chemistry effects imposed on the magnetic properties are investigated. Additionally, their role in stabilizing sub–valent Co(-I) ions are investigated. Lastly, a series of rare earth complexes bearing a tris(amido) redox–active ligand are explored to unveil emergent electronic properties when an organic radical localized on a ligand backbone is in proximity to a paramagnetic lanthanide ion. The efficacy of these complexes as catalysts for alkyl–alkyl cross–coupling catalysis and their propensity for C–H activation through sigma bond metathesis pathways are also explored.