NEW TRANSITION METAL CATALYSTS FOR CARBON-CARBON BOND FORMATION

New ligands and the reactions they enable have been the driving force of organometallic chemistry for the past decades. Since their inception, organometallic complexes have been applied to the formation of carbon-carbon bonds both as reagents and catalysts. Ligands and complexes tailored for a particular reaction have facilitated superior yields, catalytic activity, and selectivity. This dissertation focuses on two catalyst systems enabling carbon-carbon bond formation. First, the novel “sandwich” diimine copper complexes were successfully applied to the C-H insertion reaction of carbenes. This transformation facilitates the direct functionalization of alkanes without the need for an intermediate. This methodology holds the promise of more direct synthesis pathways and has drawn commensurate interest. However, carbene C-H insertion reactions are inherently challenging due to the unreactive nature of alkane C-H bonds. The field of metallocarbene C-H insertion reactions is dominated by rhodium catalysis and robust intermolecular carbene C-H insertion reactions using copper are scarce. Using copper catalysis, a number of synthetically meaningful transformations were produced. Demonstrated are novel C-H insertions of carbenes in every carbene categorization: acceptor, donor-acceptor, donor, and donor-donor. A particular focus was places on the donor and donor-donor class of carbenes as their successful application in C-H insertion methodology is exceedingly rare. Second, the utility of the novel triphenylpyridinium group in tailored transition metal catalysis was demonstrated. To demonstrate this effect the ethylene polymerization activity of a salicyliminato nickel catalyst substituted with the powerfully electron-withdrawing 2,4,6- triphenylpyridinium (trippy) group was juxtaposed to the activity of a trifluoromethyl analog. The notable advantages of this group are increased catalytic activity, increased molecular weight, improved catalyst lifetimes, and simple installation of this functional group.

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

2021

Author dc:creator

• Heidlas, Julius Xaver

Advisor dc:contributor.advisor

• Daugulis, Olafs

Committee members dc:contributor.committeemember

• Miljanić, Ognjen Š.
• Wu, Judy I-Chia
• Xu, Shoujun
• Ball, Zachary T.

• C-H insertion, metallocarbene, copper, diimine ligand, C-H functionalization, nickel olefin polymerization

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/10657/10233

OAI identifier oai:identifier

oai:uh-ir.tdl.org:10657/10233