Modulation of the Electronic Structure and Redox Properties of Lanthanide Imidophosphorane Complexes
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Boggiano, Andrew C.
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Abstract
Long characterized by their similar chemical properties and ubiquitous 3+ oxidation state, the lanthanides have recently been shown to exhibit a broader range of molecular oxidation states than previously thought possible. In 2019, terbium was reported in the 4+ oxidation state in independent reports utilizing imidophosphorane or siloxide ligand frameworks. Despite the only slightly more positive redox potential, Pr4+ proved more difficult to isolate in either of the ligands that initially supported Tb4+. In this thesis, the impact of the alkali metal cation on the redox properties of Ce3+ complexes is investigated. Additionally, a rare structurally authenticated example of Pr4+ in a low-coordinate tetrahedral environment is reported and analyzed by various physical characterization methods, including synchrotron X-ray absorption near-edge spectroscopy for the first time in a molecular complex. Further ligand development for f-element complexes is explored using La3+, due to its closed-shell electronic structure, which facilitates characterization by methods such as nuclear magnetic resonance spectroscopy. In sum, significant advances in tetravalent lanthanide chemistry are presented, and the importance of new ligand design and tuning is exemplified.
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2024-04-27
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Dissertation