Date of Award


Degree Type


Degree Name

Doctor of Philosophy



Major Professor

Brian K. Long

Committee Members

Craig Barnes, Michael Kilbey, Gila Stein


Investigating homogeneous polymerization catalysts has been a thriving area of chemistry in the academic realm for several decades now, and has helped drive the development of a range of materials, from designer plastics to cheap commodity polymers. Billions of pounds of these materials are produced every year, which ensures that continuing research in the area will be necessary to improve current processes and enable more economic use of our resources.

This dissertation showcases the Long group’s research in homogeneous polymerization catalysis and our impact on the field thus far. We show that intelligent design of redox-active catalysts allows for a unique type of control over the polymerization process, enabling the production of multiple materials from a single, welldefined species. Specifically, we first demonstrate that polyolefin branching content may be reproducibly and predictably controlled via redox-active catalysts. We then use computational and experimental methods to delve into the mechanisms that allow a redox-active catalyst to have such unique behavior. Following this, we employ this newfound insight into redox-active olefin polymerization catalysts to design our own systems that allow access to more usable polymers. This dissertation will conclude with a glimpse at ongoing research as well as a perspective on how this area of research may be improved and expanded in the future.

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