Luke, Anna2021-09-242021-09-242020-07https://hdl.handle.net/11299/224617University of Minnesota Ph.D. dissertation. July 2020. Major: Chemistry. Advisors: William Tolman, Theresa Reineke. 1 computer file (PDF); xxiii, 228 pages.Materials derived from biomass feedstocks are considered sustainable substitutes for some of the petrochemically-derived products used in commercially relevant polymers. One option for synthesizing polymers from these feedstocks involves the ring-opening polymerization (ROP) of cyclic esters, ultimately yielding degradable, aliphatic polyesters. While it is generally accepted that these polymerizations follow a coordination-insertion mechanism, by which the monomer first binds to a Lewis acid before being ring-opened via nucleophilic attack, a deeper and more fundamental mechanistic understanding of these reactions is still needed for improved catalyst design. In this work, ROP reactions are performed via a variety of Zn and Al-based catalysts with modular ligand frameworks, allowing for mechanistic investigation as a function of catalyst structure. In combination with theoretical calculations, results from these experimental works yield a better understanding of how these catalysts operate, allowing for rational catalyst design for the future.encatalyst structurecyclic estersmechanistic studyring-opening polymerizationThesis or Dissertation