{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/114025"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/114025","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Investigating metallocofactor dynamics with biomimetic dinuclear cobalt complexes","abstract":"Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2023-12-01","abstract_html":"Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2023-12-01","abstract_has_math":false,"creators":["Kelly, Kimberly A"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"M.S.","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Olshansky, Lisa"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-04-29T21:47:47Z","date_published":"2022-04-29T21:47:47Z","updated_at":"2026-07-22T22:24:54Z","subjects":["Chemistry"],"languages":["en","eng"],"rights":["Copyright 2021 Kimberly Kelly"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/114025","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Olshansky, Lisa"]},{"key":"dc:creator","label":"Author","values":["Kelly, Kimberly A"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2022-04-29T21:47:47Z","2024-04-29T21:47:53Z","2021-12","2021-12-09"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["M.S."]},{"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":["Chemistry"]}]},{"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 2021 Kimberly Kelly"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/114025"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2023-12-01","The student, Kimberly Kelly, accepted the attached license on 2021-12-09 at 08:52.","The student, Kimberly Kelly, submitted this Thesis for approval on 2021-12-09 at 08:57.","This Thesis was approved for publication on 2021-12-09 at 16:29.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17429 on 2022-04-06 at 17:18:05","Made available in DSpace on 2022-04-29T21:47:47Z (GMT). No. of bitstreams: 2 KELLY-THESIS-2021.pdf: 7634253 bytes, checksum: cd5aac5f6892de8f1d3918fb3bec8fef (MD5) LICENSE.txt: 4211 bytes, checksum: ed1b9d9cb5733a70e4d133bf829ba2ad (MD5) Previous issue date: 2021-12-09","Embargo set by: Seth Robbins for item 123390 Lift date: 2024-04-29T21:47:53Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","U of I Only","Hydrogen-bond (H-bond) networks play a critical role in nature, allowing enzymatic active sites to sequester substrates; control high-energy intermediates; and maintain structure, be it flexible or rigid. This work reports a series of dinuclear cobalt complexes: [Co2(μ–OH)2(μ-OAc)(κ1-OAc)2(pyR)4][PF6] (1R) where OAc = acetate and pyR = pyridine with para-substituent R. Complexes within the series span a range of electron-donating and withdrawing R groups, and are able to serve as structural models for a wide class of oxidase enzymes that feature an M2(µ-OH)2 diamond core. Critically, complexes within the series mimic scaffolds found in nature in that they are stabilized by H-bond interactions between μ–OH donors and κ1-OAc acceptors. The mechanism of reactivity is yet unknown, but the disruption of these networks via deprotonation has been studied in organic solvents, revealing a significant correlation between the electronics of the distal pyR upon the trans H-bonding network. The optimized conditions for the synthesis of the series are reported, and by affording the complex water-solubility via counterion exchange, the interconnected nature of solution pH and the resultant strength of the H-bonding network has also been explored. Efforts to extend the synthesis of the series into the heterobimetallic regime are not yet successful, but the presented results suggest that the μ–OH pKa can be tuned in the presence of intramolecular H-bond interactions to maintain stability and serve as a model for natural motifs."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Investigating metallocofactor dynamics with biomimetic dinuclear cobalt complexes"]}]}],"canonical_facts":{"dc:contributor":["Olshansky, Lisa"],"dc:creator":["Kelly, Kimberly A"],"dc:date":["2022-04-29T21:47:47Z","2024-04-29T21:47:53Z","2021-12","2021-12-09"],"dc:description":["Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2023-12-01","The student, Kimberly Kelly, accepted the attached license on 2021-12-09 at 08:52.","The student, Kimberly Kelly, submitted this Thesis for approval on 2021-12-09 at 08:57.","This Thesis was approved for publication on 2021-12-09 at 16:29.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17429 on 2022-04-06 at 17:18:05","Made available in DSpace on 2022-04-29T21:47:47Z (GMT). No. of bitstreams: 2 KELLY-THESIS-2021.pdf: 7634253 bytes, checksum: cd5aac5f6892de8f1d3918fb3bec8fef (MD5) LICENSE.txt: 4211 bytes, checksum: ed1b9d9cb5733a70e4d133bf829ba2ad (MD5) Previous issue date: 2021-12-09","Embargo set by: Seth Robbins for item 123390 Lift date: 2024-04-29T21:47:53Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","U of I Only","Hydrogen-bond (H-bond) networks play a critical role in nature, allowing enzymatic active sites to sequester substrates; control high-energy intermediates; and maintain structure, be it flexible or rigid. This work reports a series of dinuclear cobalt complexes: [Co2(μ–OH)2(μ-OAc)(κ1-OAc)2(pyR)4][PF6] (1R) where OAc = acetate and pyR = pyridine with para-substituent R. Complexes within the series span a range of electron-donating and withdrawing R groups, and are able to serve as structural models for a wide class of oxidase enzymes that feature an M2(µ-OH)2 diamond core. Critically, complexes within the series mimic scaffolds found in nature in that they are stabilized by H-bond interactions between μ–OH donors and κ1-OAc acceptors. The mechanism of reactivity is yet unknown, but the disruption of these networks via deprotonation has been studied in organic solvents, revealing a significant correlation between the electronics of the distal pyR upon the trans H-bonding network. The optimized conditions for the synthesis of the series are reported, and by affording the complex water-solubility via counterion exchange, the interconnected nature of solution pH and the resultant strength of the H-bonding network has also been explored. Efforts to extend the synthesis of the series into the heterobimetallic regime are not yet successful, but the presented results suggest that the μ–OH pKa can be tuned in the presence of intramolecular H-bond interactions to maintain stability and serve as a model for natural motifs."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/2142/114025"],"dc:language":["en","eng"],"dc:rights":["Copyright 2021 Kimberly Kelly"],"dc:subject":["Chemistry"],"dc:title":["Investigating metallocofactor dynamics with biomimetic dinuclear cobalt complexes"],"dc:type":["text","Thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis"],"thesis:degree_name":["M.S."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:24:54Z"}