Exploring the kinetics and thermodynamics of O–H bond activation by tripodal tris(nitroxide) aluminum and gallium complexes
Date of Award
© 2022 Joseph S. Scott. This work is freely available courtesy of the author. It may be used under the terms of the Creative Commons Attribution-ShareAlike 4.0 International (CC BY-SA 4.0) license. For all other uses, please contact the copyright holder.
Creative Commons License
This work is licensed under a Creative Commons Attribution-Share Alike 4.0 International License.
Bachelor of Arts
Chemistry & Biochemistry
Christopher R. Graves
Aluminum is one of earth’s most abundant and cheapest metals, and it is also nontoxic and environmentally friendly. This makes it an ideal candidate to be implemented in organometallic chemistry as a greener alternative to metal-based systems based on heavy and/or precious metals. One of the realms in which aluminum and other group 13 elements show promise is metal-ligand cooperative chemistry, which can afford transition metal-reminiscent small molecule activation chemistry. Our studies of organic ligands with nitroxide-functionalities within Al and Ga coordinative systems has led us to the discovery of tripodal tris(nitroxide) Al and Ga complexes with abilities to engage in metal-ligand cooperativity, including in their reaction with small molecule alcohol substrates. In an effort to better understand the mechanism of the O-H bond activation mechanism exhibited by these complexes, we report the results of various kinetics experiments that explore how alcohol O-H acidity (pKₐ) and metal center (Al, Ga) affect reaction rate, as well as an observable kinetic isotope effect. We also report the results of the screening of various alcohol substrates with these complexes, and find a strong correlation between general reactivity and alcohol acidity.
Scott, Joseph S. , '22, "Exploring the kinetics and thermodynamics of O–H bond activation by tripodal tris(nitroxide) aluminum and gallium complexes" (2022). Senior Theses, Projects, and Awards. 260.