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Computational Investigations of Organometallic Catalysis


Lawniczak, James Joseph (2023) Computational Investigations of Organometallic Catalysis. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/aepb-jm46.


Organometallic catalysis facilitates the synthesis of diverse products ranging from polyolefin materials to pharmaceutical compounds, and catalyst performance depends in part on the design of the ligand scaffold. Towards computational ligand design, quantum mechanical methods more fully capture chemical reactivity in comparison to classical methods, but are more computationally demanding. Free energy calculations of key elementary steps of the catalytic cycle permit the computational prediction of catalyst performance and allow modifications of the ligand structure to be explored. In the dissertation, experimental and computational investigations of organometallic catalysis focuses on rational ligand design. Embedding techniques such as embedded mean field theory (EMFT) and quantum mechanics/molecular mechanics (QM/MM) are leveraged in free energy calculations to allow for the reduction of wall-clock times of energy calculations and trajectory sampling. The organometallic systems investigated include Group IV polyolefin catalysts capable of co-polymerization and enantioselective cross-coupling nickel catalysts. Additionally, experimental methodology development is discussed for a nickel-catalyzed cross-coupling of alkynyl nucleophiles to tertiary electrophiles.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:organometallic catalysis, cross-coupling catalysis, polyolefin catalysis, co-polymerization, electronic structure, molecular dynamics, quantum embedding, embedded mean-field theory
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Miller, Thomas F.
Thesis Committee:
  • Miller, Thomas F.
  • Goddard, William A., III (chair)
  • Fu, Gregory C.
  • Robb, Maxwell J.
Defense Date:8 July 2022
Record Number:CaltechTHESIS:08042022-183527205
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for Chapter 3 adapted for Chapter 4 adapted for Chapter 5
Lawniczak, James Joseph0000-0003-1898-9809
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:14992
Deposited By: James Lawniczak
Deposited On:08 Aug 2022 17:26
Last Modified:20 Jun 2023 22:27

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