Electronic Theses and Dissertations

Date

2023

Document Type

Dissertation

Degree Name

Doctor of Philosophy

Department

Chemistry

Committee Chair

Timothy Brewster

Committee Member

Daniel Nascimento

Committee Member

Tomoko Fujiwara

Committee Member

Nathan DeYonker

Committee Member

Charles Garner

Abstract

Late transition metal catalysts for polymerization of olefins have drawn a significant amount of attention owing to their ability to tolerate and incorporate polar comonomers. Early-transition metals were originally used in catalyst during the polymerization of polyolefins but when interacting with oxygen the catalyst is deactivated causing issues for copolymerization with polar monomers. However, a systematic way to experimentally quantify the electronic properties of ligands used in these systems has not been developed. Quantified ligand parameters will allow for rational design of tailored polymerization catalysts which would target specific polymer properties. Heterobimetallics have become increasingly popular over the years in multiple different fields. Traditionally heterobimetallics include two transition metals allow for more versatility in applications due to the unique properties the different metals offer. The less explored area of heterobimetalics is that of one transition metal and one p-block metal such as alumnium. Incorporating a p-block metal opens more doors due to it being the most earth-abundant metal and Lewis acidity. The electronics of multiple aluminum-containing heterobimetalics are explored to discover the electronics between the aluminum and transition metal. As well as the electronics, a synthetic route is used to add aluminum to a transition metal ligand in a reliable manner. It is also reported a series of platinum complexes bearing bisphosphinemonoxide ligands which resemble those used in the polymerization catalysts of Nozaki and Chen. Their electronic properties are investigated experimentally, and trends are rationalized using computed spectral properties. The electronics are quantified to get a better understanding on how the system works to be employed in the final heterobimetallic redox switchable catalyst.

Comments

Data is provided by the student.

Library Comment

Dissertation or thesis originally submitted to ProQuest.

Notes

Open Access

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