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Olefin polymerization catalysts containing redox-active moieties that may be tuned in situ via electrochemical or chemical oxidation and reduction were synthesized and examined. The redox capable functionalities were incorporated into specifically chosen ligand frameworks and metallated using organometallic reagents so as to produce precatalysts that could be activated using methylaluminoxane, borane, or boronate-based activators. Those catalysts were shown to be active toward olefin polymerizations,their electrochemistry studied, and their in situ switchability is currently underway yielding many promising results.

Olefin polymerization catalysts containing redox-active moieties that may be tuned in situ via electrochemical or chemical oxidation and reduction were synthesized and examined. The redox capable functionalities were incorporated into specifically chosen ligand frameworks and metallated using organometallic reagents so as to produce precatalysts that could be activated using methylaluminoxane, borane, or boronate-based activators. Those catalysts were shown to be active toward olefin polymerizations,their electrochemistry studied, and their in situ switchability is currently underway yielding many promising results.

This Advances in Olefin Polymerization Catalysis symposium was held at the 247th ACS National Meeting and Exposition, March 19, 2014 in Dallas, Texas and consisted of twelve (12) invited/contributed talks. The hosting ACS division was the Division of Catalysis Science and Technology (CATL), and the specific objective of the symposium was to provide a unified, inclusive platform for the dissemination of results pertaining to polyolefin research. This was the only symposium dedicated exclusively to polyolefins and provided an opportunity for colleagues from academic institutions, national laboratories, and industry to connect and exchange ideas by which new collaborations may be established. In total we estimate that approximately 100 individuals attended this daylong symposia.

This Advances in Olefin Polymerization Catalysis symposium was held at the 247th ACS National Meeting and Exposition, March 19, 2014 in Dallas, Texas and consisted of twelve (12) invited/contributed talks. The hosting ACS division was the Division of Catalysis Science and Technology (CATL), and the specific objective of the symposium was to provide a unified, inclusive platform for the dissemination of results pertaining to polyolefin research. This was the only symposium dedicated exclusively to polyolefins and provided an opportunity for colleagues from academic institutions, national laboratories, and industry to connect and exchange ideas by which new collaborations may be established. In total we estimate that approximately 100 individuals attended this daylong symposia.

The polymerization of olefins by transition metal catalysts is an area of tremendous commercial significance and academic interest. Over the past twenty years, substantial improvements have been made in the design and industrial employment of these catalysts, especially with the development of early transition-metal metallocenes. The development of cationic (alpha-diimine)nickel(II) and palladium(II) complexes which catalyze the polymerization of both ethylene and alpha-olefins to high polymers represents a major advance in the field of olefin polymerization catalysis. Through simple variations of the alpha-diimine ligand structure and reaction conditions, the polymer molecular weights, molecular weight distributions, and microstructures can be easily controlled. The work in this dissertation focuses on olefin dimerization, oligomerization, and polymerization reactions catalyzed by (alpha-diimine)Ni(II) complexes, with the general goal of gaining an increased understanding of the mechanism of olefin polymerization by these nickel systems. Chapter Two is a study of the effects of monomer concentration, reaction temperature, aluminum cocatalyst, and electron-donating or -withdrawing diimine ligand substituents on the (alpha-diimine)Ni(II)-catalyzed oligomerization of ethylene and the dimerization of propylene. Chapters Three and Five are an account of detailed investigation of the effects of reaction conditions and diimine ligand structure on the properties of polyethylene and poly(alpha-olefin)s produced by (alpha-diimine)Ni(II) complexes. The effects of these variables on catalyst productivities, as well as polymer molecular weights and microstructures are presented.

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