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

Author: Tong, Zhengjia Jaron

Year: 2025

Degree: Dissertation (Ph.D.)

Advisor: Reisman, Sarah E.

Committee Members: Peters, Jonas C.; Reisman, Sarah E.; Hadt, Ryan G.; Fu, Gregory C.

Option: Chemistry

DOI: 10.7907/7r55-2431

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.

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