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Investigation of Ethylene Tetramerization Catalysis from Structurally-Defined Organochromium Compounds


Hirscher, Nathanael Allen (2020) Investigation of Ethylene Tetramerization Catalysis from Structurally-Defined Organochromium Compounds. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/GVYR-MV95.


Chapter 1 is a general introduction to the topic of ethylene tetramerization catalysis.

Chapter 2 presents the synthesis and catalytic utility of chromium multi-aryl complexes that were the first examples of ethylene tetramerization catalysts that could be produced without excess alkyl aluminum reagents.

Chapter 3 describes the mechanistic analysis of the ethylene tetramerization reaction using isotopically labelled ethylene. Co-production of 1-hexene along with 1-octene was determined to be intrinsic to the reaction mechanism. This is due to the intermediacy of a chromacyclic species that can either eliminate 1-hexene or insert a fourth ethylene.

Chapter 4 presents the synthesis of additional Cr tris(aryl) complexes, which are coordinatively saturated, and were used to generate a crystallographically-characterized Cr(III) cationic species. This was the first reported single-component precatalyst for ethylene tetramerization.

Chapter 5 describes the isotopic labelling of a well-defined ethylene tetramerization precatalyst with a deuteriomethyl group. This label was tracked following protonation of the neutral Cr complex via pulse EPR. Successful detection of deuterium on Cr-alkyl ligands led to in situ analysis of the catalytic mixture. A low-spin species derived from deuterated ethylene was observed.

Appendix 1 describes the synthesis of various Cr aryl amine complexes. Appendix 2 provides the results of additional catalytic experiments for ethylene tetramerization, including those with a more soluble precatalyst, and those at higher ethylene pressure. Appendix 3 details the synthesis of a molecular Re catalyst for CO2 electroreduction which was used to modify electrodes. Appendix 4 lists various X-ray crystal structures that were obtained, but not related elsewhere in the thesis.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Ethylene tetramerization, ethylene oligomerization, chromium catalysis, organometallic catalysis
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Agapie, Theodor
Thesis Committee:
  • Peters, Jonas C. (chair)
  • Grubbs, Robert H.
  • Stoltz, Brian M.
  • Agapie, Theodor
Defense Date:18 July 2019
Record Number:CaltechTHESIS:08012019-192629717
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for Chapter 2. adapted for Chapter 3. adapted for Chapter 4.
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11757
Deposited By: Nathanael Hirscher
Deposited On:20 Dec 2019 18:02
Last Modified:26 May 2021 04:39

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