In catalyst design, the ancillary ligands play a crucial role in tuning the steric and electronic structure of the system and catalyst performance. Among those ancillary ligands, neutral ligands like phosphines (PR3) or substituted pyridines are some of the most widely-used ligands in transition metal catalysis, making the study of the interaction between these ligands and the central metal necessary. While the interactions between phosphines and low oxidation state metals have been studied for decades, there are few studies concerning the interaction of those ligands with high oxidation state metals. For anionic ligands, our group has developed a new electronic parameter (Ligand Donor Parameter, LDP) using a chromium(IV) species. However, the exploration of neutral ligands with the same chromium species is not an effective method for measuring the neutral ligand donor ability. Computational studies of how neutral ligands will interact with high oxidation state metals will be presented in Chapter 2, in which a new vanadium(V) based model has been used. In Chapter 3, reactivity studies are described where we explored methods of preparing vanadium(V) complexes for donor ability measurements. These studies can give us a better understanding of neutral ligands' donor ability to the vanadium(V) metal center and extend our understanding of how these ligands interact to high oxidation state metals.
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