Date of Award
2024
Document Type
Thesis
Degree Name
Master of Science (MS)
Department
Chemistry
Committee Chair
Olaf Nachtigall
Committee Member
Carmen Scholz
Committee Member
Bernhard Vogler
Research Advisor
Olaf Nachtigall
Subject(s)
Cerium, Polyoxometalates, Ligands, Reactivity (Chemistry)
Abstract
Terminal cerium(IV)-oxo (CeIV=O) species are known to be highly reactive and tend to oligomerize and degrade organic ligands. This is preventing their application as atomic oxygen radical anion (O.-) transfer reagents. CeIV=O species have been successfully stabilized via non-covalent interactions between the oxo-group and Lewis acids. However, our work is focused on incorporating CeIV=O species into robust polyoxometalates (POMs) to avoid stabilizing the terminal oxo-group and preserving its full reaction potential. Redox-active metalloligands, such as lacunary POMs, have the capability to act as electron reservoirs and promote multi-electron redox-processes as required for catalysis. Therefore, two all-vanadium(V) dodecavanadate, {V12}, metalloligands were studied for their capabilities to act as hosts for CeIV=O species. These metalloligands were synthesized according to literature procedures. The reaction of Ce(NO3)3 and Ce(OTf)3 with the metalloligands resulted in color changes, and the obtained cerium complexes were further studied using Infrared Spectroscopy (IR), Ultraviolet-Visible Spectroscopy (UV/Vis), Nuclear Magnetic Resonance (NMR) and Cylic Voltammetry (CV) characterization techniques.
Recommended Citation
LNU, Yogesh, "Identifying redox active metalloligands for catalytic applications with special focus on enabling photoredox processes on cerium(III) centers" (2024). Theses. 680.
https://louis.uah.edu/uah-theses/680