Chiu, Hsin-Chun2021-06-292021-06-292019-04https://hdl.handle.net/11299/220611University of Minnesota Ph.D. dissertation. April 2019. Major: Chemistry. Advisor: Ian Tonks. 1 computer file (PDF); xix, 320 pages.This thesis covers two common applications of organometallic catalysis: polymerization and small molecule synthesis. The first part of my thesis, Chapters 2 and 3, discusses secondary coordination effects on Ni-catalyzed ethylene polymerizations via the development of two new families of heterobimetallic Ni complexes. The second major section, Chapter 4 and 5, is focused on selective pyrrole synthesis through the modification of our recently discovered Ti-catalyzed pyrrole synthesis from alkynes and azobenzenes. Two different strategies, stereoelectronic control and dative directing group effects, have been found to play a significant role in the chemo- and regiocontrol of this catalysis. Lastly, a new project on the combination of Pd-catalyzed polyketone formation and hydroesterification has been carried out as a novel route of making polyketoesters. Some early screenings will be presented in Chapter 6 with various diphosphine ligands.encatalysisdirecting groupethylene polymerizationheterobimetallicpyrroletitaniumThesis or Dissertation