Turning Ligands on Their Side: Computational Investigation into the Binding of N2O and N2 in Transition Metal Complexes
Date of Award
Master of Science in Natural Science
Chemistry and Biochemistry
J. Brannon Gary, Ph.D.
Brian Barngrover, Ph.D.
Russell J. Franks, Ph.D.
Alyx Frantzen, Ph.D.
Christopher Aul, Ph.D.
Common greenhouse gas nitrous oxide (N2O) is a thermodynamically potent and environmentally benign oxidant, making it a desirable target for metal center activation. Unfortunately, N2O is a poor ligand for transition metals due to its weak sigma-donating and pi-accepting properties; as a result, few transition metal complexes capable of interacting with N2O have been found. As the primary source of all nitrogen in organisms, abundant gas dinitrogen (N2) is a crucially important tiny molecule and an essential part of daily existence. However, due to its inertness, it has limited practical uses in this form. Through biological and commercial nitrogen fixation processes, one of the most inert substances, N2, is transformed into an accessible nitrogen supply, such as NH3, that may be incorporated into all nitrogen-containing biomolecules. Using computational chemistry, this work will highlight the energy differences between new potential N2O binding modes. Insights into the comparison between the k-N and k-O versus the newly reported n2-NN and n2-NO binding modes will be discussed. Through the utilization of density functional theory, a low valent cobalt complex possessing N2O in a n2-NO coordination is reported. These binding mode comparisons can be employed to develop N2O as a "green" oxidant given the limited understanding of the coordination of N2O to metal centers. This study will emphasize the energy disparities between putative N2 binding mechanisms using computational chemistry. It will also be explored how the k-N binding mode compares to the infrequently reported n2-NN binding mode. Given the partial knowledge of N2's coordination to metal centers, these binding mode comparisons can be used to improve understanding of N2's activation.
Donald, Cole, "Turning Ligands on Their Side: Computational Investigation into the Binding of N2O and N2 in Transition Metal Complexes" (2022). Electronic Theses and Dissertations. 484.
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