Authors:

Tate Michael Quinn

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About Paper:

Proton-coupled electron transfer (PCET) is an important fundamental process in biological systems utilized in energy production, oxygen formation, as well as various other enzymatic functions. Beyond biological systems, synthetic chemists have long attempted to mimic this strategy for chemical transformations including water and ammonia oxidation, both for applications in clean energy as well as creating reactive species which can initiate challenging chemical reactions. In the field of molecular inorganic chemistry, transition metals have been heavily studied in their ability to facilitate PCET reactions. In contrast, research regarding the ability of actinides to facilitate similar PCET reactivity has been underdeveloped. Our lab has demonstrated the ability for uranium(III) anilido complexes to undergo PCET to form uranium(IV) imido complexes utilizing an oxidant and a base. Further work from our lab showed the ability to undergo similar reactivity with net Hydrogen Atom Transfer (HAT) reagents. The presented work highlights the ability of various uranium(III) anilido complexes of differing electronic character, to undergo PCET reactions to form their respective uranium(IV) imido complexes. Additionally, current work shows progress towards synthesizing an ammonia-derived uranium(IV) parent imido, and even maybe an elusive uranium(V) nitrido, using traditional HAT reagents. By exploring the PCET chemistry of these species, we have been able to observe a significant metal-induced bond weakening effect determined through evaluation of the bond dissociation free energies (BDFE) of the respective N-H bonds. Keywords: Inorganic Chemistry; Actinide; PCET; Uranium

Source:

Purdue University / 2025

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Co-authors:

Tate Michael Quinn