Monometallic yttrium β-diketiminate complexes are active and controlled catalysts for perfectly alternating ring-opening copolymerization of 1-butene oxide and phthalic anhydride under mild conditions. β-Diketiminate ligands with pendant neutral donors were targeted to identify both the impact of donor strength and number of donors on rates of polymerization and the presence of undesirable side reactions. Initiating groups were also varied between alkyls, chlorides, and alkoxides. In the presence of a cocatalyst, the catalysts studied were active for polymerization with minimal side reactions, whereas lack of cocatalysts led to competing homopolymerization of epoxides. While a greater donor strength and a larger number of donors both increase the rate of polymerization, donor strength generally had a bigger impact when a cocatalyst was used. Additionally, alkoxide and chloride initiators proved to be the fastest, with alkyls being more sluggish. These subtle ligand changes significantly impacting polymerization activity lend promise to the facile tunability of rare earth metal complexes to be highly active for the target copolymerization, which renders further research in this area attractive and timely.