Spectroscopic Investigation, Kinetic Analysis, and Ligand Field Theory Rationalization of Catalytic Reactivity for Data-Driven Methodology Development

Citation

Tong, Zhengjia (2025) Spectroscopic Investigation, Kinetic Analysis, and Ligand Field Theory Rationalization of Catalytic Reactivity for Data-Driven Methodology Development. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/7r55-2431. https://resolver.caltech.edu/CaltechTHESIS:01212025-074800688

Abstract

First-row transition metal catalysis can leverage one or two-electron redox chemistry to catalyze selective C–C bond formation between two stereoelectronically differentiated substrates. Owing to this redox flexibility, many competing reaction pathways could occur, leading to the formation of both desired and undesired products. The electronic structure of the catalytic intermediates and reaction conditions are empirically recognized to modulate product distributions, but identifying the underlying design principle is often challenging. Mechanistic elucidation of the catalytic cycle and spectroscopic elucidation of important factors that influence catalytic reactivity could be beneficial to this endeavor. With the aid of ligand field theory and molecular orbital theory, a direct relationship may be established between the electronic structures of the metal catalysts and the thermodynamic or kinetic parameters of the elementary transformation they catalyze. To this end, this thesis describes the effort of combining spectroscopy, reactivity interpretation, and reaction kinetics to understand Ni-catalyzed reductive alkenylation and acylation of benzylic electrophiles and Cu-catalyzed allylic alkylation of γ-butyric lactone. The research approach and the results described herein are anticipated to aid the emergent effort of data-driven reaction development.

Item Type:

Thesis (Dissertation (Ph.D.))

Subject Keywords:

First-row transition metal catalysis, asymmetric catalysis, Ni-catalyzed reductive cross-electrophile coupling, Cu-catalyzed allylic alkylation, ligand field theory, optical spectroscopy, electrochemistry, kinetic analysis.

Degree Grantor:

California Institute of Technology

Division:

Chemistry and Chemical Engineering

Major Option:

Chemistry

Thesis Availability:

Not set

Research Advisor(s):

Reisman, Sarah E.

Thesis Committee:

Peters, Jonas C. (chair)
Reisman, Sarah E.
Hadt, Ryan G.
Fu, Gregory C.

Defense Date:

7 December 2023

Funders:

Funding Agency	Grant Number
National Institutes of Health	R35GM142595
National Institutes of Health	R35GM118191
NSF Center for Synthetic Organic Electrochemistry	CHE-2002158
Amgen	UNSPECIFIED
National Institutes of Health	R01GM080269
Dow Next Generation Educator Fund	UNSPECIFIED

Record Number:

CaltechTHESIS:01212025-074800688

Persistent URL:

https://resolver.caltech.edu/CaltechTHESIS:01212025-074800688

DOI:

10.7907/7r55-2431

Related URLs:

URL	URL Type	Description
https://doi.org/10.1002/anie.201912618	DOI	Accepted article for chapter 1
https://doi.org/10.1021/acs.inorgchem.3c02048	DOI	Accepted article for chapter 2
https://pubs.acs.org/doi/full/10.1021/jacs.3c02649	DOI	Accepted article for chapter 3
https://pubs.acs.org/doi/10.1021/jacs.4c14767	DOI	Published work relating to work described in chapter 4

ORCID:

Author	ORCID
Tong, Zhengjia	0000-0001-9329-8034

Default Usage Policy:

No commercial reproduction, distribution, display or performance rights in this work are provided.

ID Code:

16955

Collection:

CaltechTHESIS

Deposited By:

Zhengjia Tong

Deposited On:

18 Feb 2025 19:19

Last Modified:

18 Feb 2025 19:19

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