{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/124662"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/124662","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Probing the reactivity of uncommon palladium oxidation states","abstract":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2026-05-01","abstract_html":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2026-05-01","abstract_has_math":false,"creators":["Bouley, Bailey Samuel"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Mirrica, Liviu M","Girolami, Gregory S","Vura-Weis, Joshua","Fataftah, Majed"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2024,"date_issued":"2024-05","date_published":"2024-05","updated_at":"2026-07-22T22:25:02Z","subjects":["Palladium","Nickel: Cross-coupling","Organometallic","Mechanism"],"languages":["en","eng"],"rights":["Copyright 2024 Bailey Bouley"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2142/124662","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Mirrica, Liviu M","Girolami, Gregory S","Vura-Weis, Joshua","Fataftah, Majed"]},{"key":"dc:creator","label":"Author","values":["Bouley, Bailey Samuel"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2024-05","2024-04-17"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Palladium","Nickel: Cross-coupling","Organometallic","Mechanism"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en","eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2024 Bailey Bouley"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2142/124662"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2026-05-01","The student, Bailey Bouley, accepted the attached license on 2024-04-15 at 20:11.","The student, Bailey Bouley, submitted this Dissertation for approval on 2024-04-15 at 20:18.","This Dissertation was approved for publication on 2024-04-17 at 14:01.","DSpace SAF Submission Ingestion Package generated from Vireo submission #20424 on 2024-09-16 at 00:49:22","The chemistry of palladium (Pd) has been extensively interrogated in the last few decades, especially in the realm of bond forming reactions. Carbon-carbon (C-C) cross-coupling reactions are one of the most prevalent modern pharmaceutical transformations, and are commonly mediated by homogeneous Pd-based catalysts. Traditionally, most Pd cross coupling perform under a unified catalytic cycle, operating in even oxidation states (0/II) with remarkable predictability and stability. However, as we expand our repertoire of reactivity, the so-called “odd” oxidation states have garnered additional academic scrutiny, especially in photochemical and radical-based processes. Accessing this chemistry with intention has potential benefits, as (I/III) cycles could result in lower rates of β-hydride elimination due to poorer d-orbital overlap with alkyl ligands, allowing the use of sp3 reactants, and radical oxidative addition processes could allow for the use of electrophiles that cannot be easily activated with classical Pd catalysts. Despite these potential benefits, the unstable nature of Pd(I) and Pd(III) complexes makes characterization of these ions difficult, and our understanding of how odd oxidation state Pd complexes react is limited. Our group has shown that pyridinophane macrocycles can be used to stabilize these oxidation states to probe their reactivity by creating a distorted octahedral geometry around the metal ion. This strategy has been expanded upon in this document to explore not only the high, but also the low-valent chemistry in the areas of Pd(I/III) catalytic transformations and C-H activation. These results help to better frame the general reactivity principles of these uncommon palladium oxidation states."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Probing the reactivity of uncommon palladium oxidation states"]}]}],"canonical_facts":{"dc:contributor":["Mirrica, Liviu M","Girolami, Gregory S","Vura-Weis, Joshua","Fataftah, Majed"],"dc:creator":["Bouley, Bailey Samuel"],"dc:date":["2024-05","2024-04-17"],"dc:description":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2026-05-01","The student, Bailey Bouley, accepted the attached license on 2024-04-15 at 20:11.","The student, Bailey Bouley, submitted this Dissertation for approval on 2024-04-15 at 20:18.","This Dissertation was approved for publication on 2024-04-17 at 14:01.","DSpace SAF Submission Ingestion Package generated from Vireo submission #20424 on 2024-09-16 at 00:49:22","The chemistry of palladium (Pd) has been extensively interrogated in the last few decades, especially in the realm of bond forming reactions. Carbon-carbon (C-C) cross-coupling reactions are one of the most prevalent modern pharmaceutical transformations, and are commonly mediated by homogeneous Pd-based catalysts. Traditionally, most Pd cross coupling perform under a unified catalytic cycle, operating in even oxidation states (0/II) with remarkable predictability and stability. However, as we expand our repertoire of reactivity, the so-called “odd” oxidation states have garnered additional academic scrutiny, especially in photochemical and radical-based processes. Accessing this chemistry with intention has potential benefits, as (I/III) cycles could result in lower rates of β-hydride elimination due to poorer d-orbital overlap with alkyl ligands, allowing the use of sp3 reactants, and radical oxidative addition processes could allow for the use of electrophiles that cannot be easily activated with classical Pd catalysts. Despite these potential benefits, the unstable nature of Pd(I) and Pd(III) complexes makes characterization of these ions difficult, and our understanding of how odd oxidation state Pd complexes react is limited. Our group has shown that pyridinophane macrocycles can be used to stabilize these oxidation states to probe their reactivity by creating a distorted octahedral geometry around the metal ion. This strategy has been expanded upon in this document to explore not only the high, but also the low-valent chemistry in the areas of Pd(I/III) catalytic transformations and C-H activation. These results help to better frame the general reactivity principles of these uncommon palladium oxidation states."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/124662"],"dc:language":["en","eng"],"dc:rights":["Copyright 2024 Bailey Bouley"],"dc:subject":["Palladium","Nickel: Cross-coupling","Organometallic","Mechanism"],"dc:title":["Probing the reactivity of uncommon palladium oxidation states"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:02Z"}