Degree

Doctor of Philosophy (PhD)

Department

Department of Chemistry

Document Type

Dissertation

Abstract

Alkyne metathesis has experienced significant growth in the number of efficient catalysts over the last three decades, and the reaction has found broad applications in the synthesis of polymers, natural products, and supramolecular materials. Chapter 1 reviews the historical development and mechanism of alkyne metathesis as well as the evolution of well-defined alkyne metathesis catalysts and their applications.

Chapter 2 discusses the fine-tuning of fluoroalkoxy-based alkyne metathesis catalysts.  A series of Mo-based alkylidyne complexes bearing a bidentate fluorinated ligand have been synthesized and their performance tested. The study investigates how the electrophilicity of metal complexes and ligand design affect their activity towards alkyne metathesis.

Chapter 3 explores cycloparaphenyleneacetylene (CPPA), arynes, and adibocyclooctynes as new monomers for ring-opening alkyne metathesis polymerization using fluoroalkoxide-supported Mo (VI) alkylidynes as initiators. Preliminary experimental and computational studies are conducted to evaluate the feasibility of the proposed polymerizations. The goal is to develop a catalyst/monomer system that allows for the preparation of conjugated polymers with low polydispersity under chain growth/living conditions.

Chapter 4 focuses on the development and application of Re (V) alkylidynes for alkyne metathesis. Rhenium alkylidynes are demonstrated to facilitate macrocyclization reactions that were previously inaccessible with molybdenum and tungsten systems. In addition, kinetic studies are conducted to provide insight into the reactivity of the alkylidynes.

Date

7-17-2026

Committee Chair

Dr. Semin Lee

LSU Acknowledgement

1

LSU Accessibility Acknowledgment

1

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Available for download on Friday, July 15, 2033

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