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Improvement of Olefin Metathesis Efficiency through Understanding Catalyst Stability


Hong, Soon Hyeok (2007) Improvement of Olefin Metathesis Efficiency through Understanding Catalyst Stability. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/QMZ9-3Y05.


The recent development of ruthenium olefin metathesis catalysts, which show high activity and functional group tolerance, has expanded the scope of olefin metathesis. To improve efficiency of the ruthenium-catalyzed olefin metathesis, this dissertation describes: (1) mechanistic study to understand decomposition pathways of ruthenium olefin metathesis catalysts for the development of more stable and efficient catalysts, (2) a method to prevent an undesirable side reaction for the improvement of selectivity of ruthenium-catalyzed olefin metathesis, and (3) a novel ruthenium catalyst to increase olefin metathesis efficiency in aqueous media for potential biological applications and environmentally friendly approaches to this chemistry.

Chapter 2 describes the first well-characterized decomposition products, dinuclear ruthenium hydride complex and methylphosphonium salt, from an N-heterocyclic carbene-based ruthenium catalyst under typical metathesis conditions. In Chapter 3, the decomposition study was expanded to other widely used ruthenium olefin metathesis catalysts. Phosphine-involvement in the decomposition was consistently observed whether or not an olefin was present. The presence of other decomposition modes for phosphine-free ruthenium catalysts was also described. Chapter 4 addresses another decomposition pathway of an N,N’-diphenylbenzimidazol-2-ylidene-based catalyst via C--H activation. Chapter 6 describes the development of a novel poly(ethylene glycol)-supported water-soluble catalyst, which is active and stable in aqueous media. Chapter 7 describes an efficient, practical, and environmentally friendly method to remove residual ruthenium-containing byproducts by simple aqueous workup from olefin metathesis products using the poly(ethylene glycol)-supported catalyst.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:aqueous olefin metathesis; decomposition; N-heterocyclic carbene; olefin metathesis; ruthenium; ruthenium removal; stability; water-soluble catalyst
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)
  • Stoltz, Brian M.
  • Tirrell, David A.
  • Grubbs, Robert H.
Defense Date:22 March 2007
Non-Caltech Author Email:pureston (AT)
Record Number:CaltechETD:etd-04022007-122855
Persistent URL:
Hong, Soon Hyeok0000-0003-0605-9735
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:1250
Deposited By: Imported from ETD-db
Deposited On:02 May 2007
Last Modified:03 Mar 2020 00:10

Thesis Files

PDF (Thesis_SHHong.pdf) - Final Version
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