{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21894"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21894","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Studies of the mechanism of oxygen atom transfer from molecular oxygen to iridium-coordinated cyclooctadiene","abstract":"The cyclooctadiene complex ((C$\\sb8$H$\\sb{12}$)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, a, reacted in solution at ambient temperature with O$\\sb2$ to form ((C$\\sb8$H$\\sb{11}$OH)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, f. Sealed tube $\\sp{31}$P NMR spectroscopic experiments established the presence of three additional species in this reaction and the relationship between them. One of these intermediates, the oxametallacyclobutane complex ((C$\\sb8$H$\\sb{12}$O)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, e, was isolated and structurally characterized. Pseudo-octahedral coordination geometry at the Ir(III) center is defined by three terminal (P$\\sb3$O$\\sb9$)$\\sp{3-}$ oxygen atoms, an olefinic C=C bond, and the carbon and oxygen atoms of an oxametallacyclobutane ring. The structures a and e are related by insertion of an O atom into a C-Ir bond of a. The structures of e and f are related by proton transfer from the allylic carbon of e to the oxygen atom of the oxametallacyclobutane ring. Oxygen uptake experiments indicated that both atoms of O$\\sb2$ are incorporated into a molecule of a.","abstract_html":"The cyclooctadiene complex ((C$\\sb8$H$\\sb{12}$)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, a, reacted in solution at ambient temperature with O$\\sb2$ to form ((C$\\sb8$H$\\sb{11}$OH)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, f. Sealed tube $\\sp{31}$P NMR spectroscopic experiments established the presence of three additional species in this reaction and the relationship between them. One of these intermediates, the oxametallacyclobutane complex ((C$\\sb8$H$\\sb{12}$O)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, e, was isolated and structurally characterized. Pseudo-octahedral coordination geometry at the Ir(III) center is defined by three terminal (P$\\sb3$O$\\sb9$)$\\sp{3-}$ oxygen atoms, an olefinic C=C bond, and the carbon and oxygen atoms of an oxametallacyclobutane ring. The structures a and e are related by insertion of an O atom into a C-Ir bond of a. The structures of e and f are related by proton transfer from the allylic carbon of e to the oxygen atom of the oxametallacyclobutane ring. Oxygen uptake experiments indicated that both atoms of O$\\sb2$ are incorporated into a molecule of a.","abstract_has_math":true,"creators":["Lockledge, Scott Potter"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Klemperer, Walter G."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:22:26Z","date_published":"2011-05-07T13:22:26Z","updated_at":"2026-07-22T22:25:18Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1990 Lockledge, Scott Potter"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9114327","(UMI)AAI9114327"],"render_values":[{"text":"AAI9114327","href":null,"code":true},{"text":"(UMI)AAI9114327","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21894","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Klemperer, Walter G."]},{"key":"dc:creator","label":"Author","values":["Lockledge, Scott Potter"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:22:26Z","10000-01-01","1990"]},{"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":["Chemistry, Inorganic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1990 Lockledge, Scott Potter"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9114327","(UMI)AAI9114327","http://hdl.handle.net/2142/21894"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The cyclooctadiene complex ((C$\\sb8$H$\\sb{12}$)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, a, reacted in solution at ambient temperature with O$\\sb2$ to form ((C$\\sb8$H$\\sb{11}$OH)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, f. Sealed tube $\\sp{31}$P NMR spectroscopic experiments established the presence of three additional species in this reaction and the relationship between them. One of these intermediates, the oxametallacyclobutane complex ((C$\\sb8$H$\\sb{12}$O)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, e, was isolated and structurally characterized. Pseudo-octahedral coordination geometry at the Ir(III) center is defined by three terminal (P$\\sb3$O$\\sb9$)$\\sp{3-}$ oxygen atoms, an olefinic C=C bond, and the carbon and oxygen atoms of an oxametallacyclobutane ring. The structures a and e are related by insertion of an O atom into a C-Ir bond of a. The structures of e and f are related by proton transfer from the allylic carbon of e to the oxygen atom of the oxametallacyclobutane ring. Oxygen uptake experiments indicated that both atoms of O$\\sb2$ are incorporated into a molecule of a.","Two other species were observed by $\\sp{13}$C and $\\sp{31}$P NMR spectroscopy and structures for these complexes are proposed. On the basis of these observations, a mechanism is proposed detailing the incorporation of the oxygen atoms from O$\\sb{2}$ into a and its subsequent reactivity.","Made available in DSpace on 2011-05-07T13:22:26Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9114327.pdf: 3890413 bytes, checksum: e1723df5b022b6579aeb0d9397f73ea5 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:53:55Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:24:59-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Studies of the mechanism of oxygen atom transfer from molecular oxygen to iridium-coordinated cyclooctadiene"]}]}],"canonical_facts":{"dc:contributor":["Klemperer, Walter G."],"dc:creator":["Lockledge, Scott Potter"],"dc:date":["2011-05-07T13:22:26Z","10000-01-01","1990"],"dc:description":["The cyclooctadiene complex ((C$\\sb8$H$\\sb{12}$)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, a, reacted in solution at ambient temperature with O$\\sb2$ to form ((C$\\sb8$H$\\sb{11}$OH)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, f. Sealed tube $\\sp{31}$P NMR spectroscopic experiments established the presence of three additional species in this reaction and the relationship between them. One of these intermediates, the oxametallacyclobutane complex ((C$\\sb8$H$\\sb{12}$O)Ir(P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9$)$\\sb4$N) $\\sb2$, e, was isolated and structurally characterized. Pseudo-octahedral coordination geometry at the Ir(III) center is defined by three terminal (P$\\sb3$O$\\sb9$)$\\sp{3-}$ oxygen atoms, an olefinic C=C bond, and the carbon and oxygen atoms of an oxametallacyclobutane ring. The structures a and e are related by insertion of an O atom into a C-Ir bond of a. The structures of e and f are related by proton transfer from the allylic carbon of e to the oxygen atom of the oxametallacyclobutane ring. Oxygen uptake experiments indicated that both atoms of O$\\sb2$ are incorporated into a molecule of a.","Two other species were observed by $\\sp{13}$C and $\\sp{31}$P NMR spectroscopy and structures for these complexes are proposed. On the basis of these observations, a mechanism is proposed detailing the incorporation of the oxygen atoms from O$\\sb{2}$ into a and its subsequent reactivity.","Made available in DSpace on 2011-05-07T13:22:26Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9114327.pdf: 3890413 bytes, checksum: e1723df5b022b6579aeb0d9397f73ea5 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:53:55Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:24:59-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9114327","(UMI)AAI9114327","http://hdl.handle.net/2142/21894"],"dc:language":["eng"],"dc:rights":["Copyright 1990 Lockledge, Scott Potter"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Studies of the mechanism of oxygen atom transfer from molecular oxygen to iridium-coordinated cyclooctadiene"],"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":"2026-07-22T22:25:18Z"}