Fundamental Studies of the Reactivity of Transition Metal Hydrides with Carbon Dioxide and Related Hydride Acceptors

Date of Award

Spring 2022

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Hazari, Nilay

Abstract

This dissertation describes the mechanistic investigation of hydride transfer from transition metal hydrides to carbon dioxide and related hydride acceptors. Hydride transfer is studied through both empirical methods that use structure-activity relationships and, quantitative thermodynamic and kinetic studies that focus on fundamental reactivity. Chapter 1 provides a review of work done to understand the reactivity of metal hydrides. It discusses empirical structure activity relationships developed with transition metal hydrides bound by a pincer ligand. This chapter also covers thermodynamic and kinetic hydricity and how they have been used to investigate the reactivity of metal hydrides. It ends with a brief discussion of linear free energy relationships which have been used to predict catalyst kinetics using thermodynamics. Chapter 2 focuses on empirical investigations performed on the catalytic hydroboration of CO2 using transition metal hydride pincer complexes. Through structure-activity relationships, the factors that influence catalyst selectivity are established. Chapter 3 discusses the development of linear free energy relationships for hydride transfer reactions to CO2 and related hydride acceptors using thermodynamic and kinetic hydricities. It also discusses how steric differences make predicting kinetics from thermodynamic hydricity challenging. Finally, Chapter 4 explores the relative catalytic activity of commercially available Suzuki-Miyaura cross coupling precatalysts.

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