{"id":{"repo_id":"gatech","oai_identifier":"oai:repository.gatech.edu:1853/81570"},"canonical_url":"https://search.dev.ndltd.org/etd/gatech/oai:repository.gatech.edu:1853/81570","repository":{"repo_id":"gatech","name":"Georgia Tech","base_url":"https://repository.gatech.edu/server/oai/request"},"display":{"title":"Transuranic Imidophosphorane Chemistry","abstract":"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.","abstract_html":"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.","abstract_has_math":false,"creators":["Otte, Kaitlyn Sue"],"institution":"Georgia Institute of Technology","degree_name":null,"degree_level":"Doctoral","degree_discipline":null,"degree_department":"Chemistry and Biochemistry","school":null,"contributors":[],"advisors":["Kurfess, Thomas R."],"committee_chairs":[],"committee_members":["Soper, Jake D.","Sadighi, Joseph P.","Wilkinson, Angus P.","Erickson, Anna S."],"year":2025,"date_issued":"2025-04-29","date_published":"2025-04-29","updated_at":"2026-07-27T19:50:08Z","subjects":["actinides","transuranic","coordination chemistry","neptunium","plutonium","ligand design","proton-coupled electron transfer","electrochemistry","redox reactions"],"languages":["en_US"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1853/81570","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Kurfess, Thomas R."]},{"key":"dc:contributor.committeemember","label":"Committee Member","values":["Soper, Jake D.","Sadighi, Joseph P.","Wilkinson, Angus P.","Erickson, Anna S."]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry and Biochemistry"]},{"key":"dc:creator","label":"Author","values":["Otte, Kaitlyn Sue"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2026-05-21T20:44:35Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2026-05-21T20:44:35Z"]},{"key":"dc:date.issued","label":"Date","values":["2025-04-29"]},{"key":"dc:publisher","label":"Institution","values":["Georgia Institute of Technology"]},{"key":"dc:type","label":"Dc Type","values":["Text"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Doctoral"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["actinides","transuranic","coordination chemistry","neptunium","plutonium","ligand design","proton-coupled electron transfer","electrochemistry","redox reactions"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en_US"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/1853/81570"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["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."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph.D."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Transuranic Imidophosphorane Chemistry"]}]}],"canonical_facts":{"dc:contributor.advisor":["Kurfess, Thomas R."],"dc:contributor.committeemember":["Soper, Jake D.","Sadighi, Joseph P.","Wilkinson, Angus P.","Erickson, Anna S."],"dc:contributor.department":["Chemistry and Biochemistry"],"dc:creator":["Otte, Kaitlyn Sue"],"dc:date.accessioned":["2026-05-21T20:44:35Z"],"dc:date.available":["2026-05-21T20:44:35Z"],"dc:date.issued":["2025-04-29"],"dc:description.abstract":["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."],"dc:description.degree":["Ph.D."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["https://hdl.handle.net/1853/81570"],"dc:language.iso":["en_US"],"dc:publisher":["Georgia Institute of Technology"],"dc:subject":["actinides","transuranic","coordination chemistry","neptunium","plutonium","ligand design","proton-coupled electron transfer","electrochemistry","redox reactions"],"dc:title":["Transuranic Imidophosphorane Chemistry"],"dc:type":["Text"],"thesis:degree_level":["Doctoral"]},"updated_at":"2026-07-27T19:50:08Z"}