Transuranic Imidophosphorane Chemistry

Since 2019, the La Pierre group has introduced multiple new molecular oxidation states to for the lanthanide series, namely Tb4+, Pr4+, and Pr5+. This was achieved through strategic ligand development, where these imidophosphorane ligands helped to substantially cathodically shift the redox couples of the lanthanides, facilitating the isolation of these unique compounds. Herein, we present the expansion of this work to the actinides to study the molecular and electronic structures of transuranic imidophosphorane compounds. The isolation, characterization, and redox chemistry of a large isostructural family of Ce, U, Np, and Pu complexes is presented. These compounds offer a unique opportunity to map the influence bonding has on a series of compounds that show a large change in chemical reactivity and kinetics, while maintaining very similar electrochemical potentials. Notably, this family boasts the first tetrahedral, non-actinyl Np(V) complex along with exhibiting a new fundamental reaction pathway for transuranic chemistry. Namely a firstorder proton-coupled electron transfer (PCET) reaction and we demonstrate PCET reactivity as a measure of covalency for this imidophosphorane family.

Level thesis:degree_level

Doctoral

Department dc:contributor.department

Chemistry and Biochemistry

Grantor dc:publisher

Georgia Institute of Technology

Year dc:date.issued

2025

Author dc:creator

• Otte, Kaitlyn Sue

Advisor dc:contributor.advisor

• Kurfess, Thomas R.

Committee members dc:contributor.committeemember

• Soper, Jake D.
• Sadighi, Joseph P.
• Wilkinson, Angus P.
• Erickson, Anna S.

• actinides
• transuranic
• coordination chemistry
• neptunium
• plutonium
• ligand design
• proton-coupled electron transfer
• electrochemistry
• redox reactions

Language dc:language.iso

en_US

Handle dc:identifier.uri

https://hdl.handle.net/1853/81570

OAI identifier oai:identifier

oai:repository.gatech.edu:1853/81570