Small Molecule Reactivity of Trisphosphine-Supported Iron and Cobalt Complexes

• Main Author: Deegan, Meaghan Marie
• Format: Others
• Language: en
• Published: 2020
• Online Access: https://thesis.library.caltech.edu/11801/13/Combined.pdf; Deegan, Meaghan Marie (2020) Small Molecule Reactivity of Trisphosphine-Supported Iron and Cobalt Complexes. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/QDAW-M003. https://resolver.caltech.edu/CaltechTHESIS:09252019-210323106 <https://resolver.caltech.edu/CaltechTHESIS:09252019-210323106>

<p>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.</p>