Small Molecule Reactivity of Trisphosphine-Supported Iron and Cobalt Complexes

Author: Deegan, Meaghan Marie

Year: 2020

Degree: Dissertation (Ph.D.)

Advisor: Peters, Jonas C.

Committee Members: Agapie, Theodor; Fu, Gregory C.; Reisman, Sarah E.; Peters, Jonas C.

Option: Chemistry

DOI: 10.7907/QDAW-M003

Abstract

The work described in this thesis emphasizes accessing novel reactivity patterns in the activation of carbon monoxide, dinitrogen, and dihydrogen by leveraging phosphine-supported iron and cobalt complexes. In Chapters 2 and 3, systems that access CO and N₂ reductive functionalization from highly reduced Fe-hydride precursors are described. These systems access productive C-H and N-H bond forming steps from hydride precursors that ultimately allows for the liberation of four-electron reduced products through novel chemical pathways. Chapter 4 describes an unusual example of a terminal cobalt carbyne through the O-functionalization of a carbonyl complex. Next, in Chapter 5, we consider electronically unusual examples of dihydrogen complexes and explore their propensity for accessing H-atom and hydride transfer. Finally, to conclude, Chapter 6 details our synthetic efforts targeting the synthesis of a terminal Fe-carbide complex through the cleavage of a thiocarbonyl precursor.

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