Investigating Steric And Electronic Factors In The Synthesis Of Complexes Containing Tetravalent Cerium-Ligand Multiple Bonds

Complexes featuring multiple bonds between d-block transition metals and ligand fragments have well-established chemistry. These bonds have been shown to exhibit interesting catalytic transformations or act as important ancillary ligands. However, the chemistry of analogous complexes involving the rare-earth elements is under-developed. This dissertation explores the synthetic strategies that were employed in isolating unique examples of Ce=N complexes supported by the TriNOx3– ligand framework. We performed the first comprehensive study of a series cerium-imido complexes and documented the effects of capping alkali-metal cations on the solid state and electronic structures of Ce=N bond. Finally, preliminary reactivity studies on the alkali-metal capped Ce=N complexes afforded isolation of rare examples of complexes featuring Ce=O bonds.