Date of Award

2021

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Abstract

Catalysis is an integral part of society, which is often taken for granted. Over the past few years, there has been an increased effort to develop catalysts that are more environmentally friendly, selective, and energy efficient. This work focuses on the development of novel complexes made from a carefully designed non-innocent ligand together with earth-abundant and cost-effective transition metals that can be used to understand fundamental inorganic chemistry principles and serve as model systems. The work reported within validates the utility of this novel class of redox non-innocent ligand to form metal complexes with interesting properties, such as a non-porphyrin based spin-admixed FeIII species. This new class of carbazole-based ligand has been extremely useful in supporting the formation of a multitude of interesting species, including an iron-dinitrogen complex that can serve as model for nitrogenase and catalytically produce ammonia. Other unique complexes include a 1D iron-azide bridged single molecule magnet, a FeIII species used to study Lewis acid-carbonyl interactions, and a µ-nitrido bridged VVI dimer that is surprisingly stable. A variety of techniques such as SQUID magnetometry, X-ray crystallography, and cyclic voltammetry (CV), along with infrared (IR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), UV-Visible (UV-Vis), and Mossbauer spectroscopy, have been used to prove that our novel ligand system is indeed non-innocent and provides an easily-tunable scaffold that can support a variety of transition metal complexes that have applications ranging from catalysis to active site modeling.

Creative Commons License

Creative Commons Attribution-Noncommercial-No Derivative Works 3.0 License
This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 3.0 License.

Available for download on Thursday, February 02, 2023

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