Date of Award

Fall 1-1-2025

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Holland, Patrick

Abstract

This thesis describes the discovery and mechanistic studies of cobalt- and iron-catalyzed alkene hydrofunctionalization reactions. Chapter 1 introduces the fields of alkene hydrofunctionalization via metal-catalyzed hydrogen atom transfer (MHAT) and first-row transition metal-catalyzed alkene dicarbofunctionalization. Chapter 2 describes a method for intermolecular hydroalkoxylation and hydrocarboxylation of 2-azadienes using oxidative cobalt-catalyzed hydrogen atom transfer. The method generates 2-azaallyl cation equivalents under mild conditions to yield hemiaminal ethers and esters, and is chemoselective for 2-azadienes in the presence of other C=C double bonds. Chapter 3 describes the synthesis, characterization, and reactivity of an isolable alkylcobalt complex that models an intermediate proposed in oxidative MHAT catalysis. Isolation of the complex enabled its structural characterization, comparison of electronic structure to a related alkylcobalt complex, and reactivity studies with different nucleophiles. The electrophilic reactivity of the complex in the presence of nucleophiles supported its proposed role in oxidative MHAT catalysis as a carbocation surrogate. Chapter 4 describes the identification of iron-containing species in an iron-catalyzed alkene dicarbofunctionalization method. Through Mössbauer spectroscopy and density functional theory calculations, three species were identified and are proposed to act as catalyst reservoirs.

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