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Selectivity in ruthenium catalyzed olefin metathesis : applications and origins

Citation

Keitz, Benjamin Keith (2013) Selectivity in ruthenium catalyzed olefin metathesis : applications and origins. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:07312012-134600191

Abstract

Ruthenium-based catalysts for olefin metathesis display high activity in the presence of common functional groups and have been utilized in a variety of chemical disciplines. This thesis describes the development of new catalysts with superior properties and mechanistic studies directed at understanding the factors governing catalyst activity and selectivity.

Chapter 2 describes the preparation of acid-activated olefin metathesis catalysts containing acetylacetonate (acac)-type ligands. The effect of ligand structure and the exogenous acid on catalytic activity was examined. The acid-activated catalysts were also combined with a photoacid generator (PAG), which resulted in a highly active system for photo-activated olefin metathesis.

Chapter 3 details the incorporation of mesoionic carbenes (MICs) into ruthenium metathesis catalysts. The activity of these catalysts in several metathesis assays was measured and correlated to their initiation rates. The protonolysis of a Ru-MIC bond and the incorporation of this reaction into an acid-activated catalyst are also described.

Chapter 4 explores the relationship between catalyst structure and degenerate metathesis. A ring-closing metathesis assay was used to measure the preference of different catalysts for productive or degenerate metathesis. The relationship between degenerate metathesis and reactions such as ethenolysis is also discussed.

Chapter 5 describes the study of ruthenacyclobutanes formed from the degenerate metathesis selective catalysts presented in Chapter 4. The rates of various chemical exchange processes were measured and correlated to catalyst structure. Kinetic parameters for the rate-limiting step in ring-closing metathesis were also measured and used to rationalize the differences in productive/degenerate selectivity for various catalysts.

Chapter 6 details the preparation and study of C-H-activated ruthenium catalysts for Z-selective olefin metathesis. Ligand effects on catalyst activity and selectivity are explored along with the application of these catalysts in Z-selective cross-metathesis and ring-opening metathesis polymerization.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:organometallic chemistry, olefin metathesis, ruthenium
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Grubbs, Robert H.
Thesis Committee:
  • Bercaw, John E. (chair)
  • Peters, Jonas C.
  • Stoltz, Brian M.
  • Grubbs, Robert H.
Defense Date:18 July 2012
Author Email:bkkeitz (AT) gmail.com
Funders:
Funding AgencyGrant Number
National Institute of HealthNIH 5R01GM031332-27
National Science FoundationCHE-1048404
National Defense Science and Engineering Graduate FellowshipUNSPECIFIED
Record Number:CaltechTHESIS:07312012-134600191
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:07312012-134600191
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:7181
Collection:CaltechTHESIS
Deposited By: Benjamin Keitz
Deposited On:30 Aug 2012 18:35
Last Modified:03 Jul 2014 20:43

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