Polymerization and Isomerization of Olefins using Late-Transition Metal Complexes

Late-transition metal complexes serve as efficient olefin polymerization catalysts. The mechanism of α-diimine-palladium and nickel catalyzed olefin polymerization is well understood. By understanding the fundamental steps of olefin polymerization, catalysts can be rationally designed to achieve a polymer with desired properties. This dissertation focuses on understanding these fundamental steps in order to design complexes that serve as olefin polymerization and isomerization catalysts. Sandwich-diimine palladium catalysts were used to selectively isomerize 1-olefins to 2-olefins. By activating the palladium catalyst with phenylsilane and NaBArF, a broad range of olefins were isomerized at low catalyst loadings and low temperatures. Mechanistic studies show that regioselectivity is determined by selective displacement of bound internal olefin by a terminal olefin from palladium. Phenanthroline based palladium catalysts were shown to catalyzed a chain running isomerization of olefins. By changing the steric properties of the ligand, but using similar reaction conditions, an alternate, thermodynamic regioselectivity was obtained. A wide range of substrates were isomerized to produce synthetically useful products. The reaction is scalable with very low catalyst loadings. A new monodentate phosphine nickel complex was synthesized and shown to be an efficient olefin polymerization catalyst. The catalyst produced ultrahigh-molecular weight polyethylene and had a turnover frequency that is equivalent to the most active late-transition metal olefin polymerization catalysts. However, a short lifetime was observed and polymerization must be performed at room temperature or below.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

Doctoral

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Houston

Year dc:date.issued

2019

Author dc:creator

• Kocen, Andrew Lewis 1992-

Advisor dc:contributor.advisor

• Daugulis, Olafs

Committee members dc:contributor.committeemember

• May, Jeremy A.
• Wu, Judy I-Chia
• Teets, Thomas S.
• Robertson, Megan L.

• Organometallic chemistry
• Polymer Chemistry
• Organic chemistry
• Olefin Isomerization
• Ultrahigh-molecular weight polyethylene

Statement dc:rights

• The author of this work is the copyright owner. UH Libraries and the Texas Digital Library have their permission to store and provide access to this work. UH Libraries has secured permission to reproduce any and all previously published materials contained in the work. Further transmission, reproduction, or presentation of this work is prohibited except with permission of the author(s).

Language dc:language.iso

eng

Handle dc:identifier.uri

https://hdl.handle.net/10657/5307

OAI identifier oai:identifier

oai:uh-ir.tdl.org:10657/5307