{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/72287"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/72287","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 Carbon Oxygen Bond Formation in a Polyoxoanion-Supported Oxairidacyclobutane Complex","abstract":"The goal of this research has been to understand the C-O bond formation mechanism of the oxametallacyclobutane complex, ((C$\\sb8$H$\\sb $O)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (2). The reaction of ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (1) with cyanoolefins was carried out in order to synthesize bidentate (P$\\sb3$O$\\sb9)\\sp{3-}$ complexes, ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp2$O-P$\\sb3$O$\\sb9$)(cyanoolefin)) ((n-$\\rm C\\sb4H\\sb9)\\sb4N\\rbrack\\sb{2}$. The $\\sp{31}$P chemical shifts observed for these complexes were then used to assign the $\\sp{31}$P NMR shifts observed for an intermediate in the formation of 2 by O$\\sb2$ oxidation of 1. The reaction of ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ with O$\\sb2$ has been further investigated to study the conversion of the previously observed intermediate to complex 2. Compound ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ reacted with allyl iodide to form a $\\sigma$-allyl complex, ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9)(\\eta\\sp1$-C$\\sb3$H$\\sb5$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N). This reaction was performed to examine the equilibrium between tridentate trimetaphosphate coordination and bidentate coordination, when both modes are allowed by the 18-electron rule. Finally, a unique reversible conversion of the oxametallacyclobutane complex 2 to the aquo olefin complex ((C$\\sb8$H$\\sb $)Ir(OH$\\sb2)(\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) (3) is reported. The investigation of the interconversion pathway leads to the observation and characterization of two intermediates and offers a clearer view of the mechanism by which complex 2 is formed.","abstract_html":"The goal of this research has been to understand the C-O bond formation mechanism of the oxametallacyclobutane complex, ((C$\\sb8$H$\\sb $O)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (2). The reaction of ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (1) with cyanoolefins was carried out in order to synthesize bidentate (P$\\sb3$O$\\sb9)\\sp{3-}$ complexes, ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp2$O-P$\\sb3$O$\\sb9$)(cyanoolefin)) ((n-$\\rm C\\sb4H\\sb9)\\sb4N\\rbrack\\sb{2}$. The $\\sp{31}$P chemical shifts observed for these complexes were then used to assign the $\\sp{31}$P NMR shifts observed for an intermediate in the formation of 2 by O$\\sb2$ oxidation of 1. The reaction of ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ with O$\\sb2$ has been further investigated to study the conversion of the previously observed intermediate to complex 2. Compound ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ reacted with allyl iodide to form a <span class=\"etd-inline-math\">&sigma;</span>-allyl complex, ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9)(\\eta\\sp1$-C$\\sb3$H$\\sb5$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N). This reaction was performed to examine the equilibrium between tridentate trimetaphosphate coordination and bidentate coordination, when both modes are allowed by the 18-electron rule. Finally, a unique reversible conversion of the oxametallacyclobutane complex 2 to the aquo olefin complex ((C$\\sb8$H$\\sb $)Ir(OH$\\sb2)(\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) (3) is reported. The investigation of the interconversion pathway leads to the observation and characterization of two intermediates and offers a clearer view of the mechanism by which complex 2 is formed.","abstract_has_math":true,"creators":["Chen, Jie"],"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":2014,"date_issued":"2014-12-17T21:29:10Z","date_published":"2014-12-17T21:29:10Z","updated_at":"2026-07-22T22:26:06Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI9411582"],"render_values":[{"text":"(UMI)AAI9411582","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/72287","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":["Chen, Jie"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-17T21:29:10Z","10000-01-01","1993"]},{"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":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/72287","(UMI)AAI9411582"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The goal of this research has been to understand the C-O bond formation mechanism of the oxametallacyclobutane complex, ((C$\\sb8$H$\\sb $O)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (2). The reaction of ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (1) with cyanoolefins was carried out in order to synthesize bidentate (P$\\sb3$O$\\sb9)\\sp{3-}$ complexes, ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp2$O-P$\\sb3$O$\\sb9$)(cyanoolefin)) ((n-$\\rm C\\sb4H\\sb9)\\sb4N\\rbrack\\sb{2}$. The $\\sp{31}$P chemical shifts observed for these complexes were then used to assign the $\\sp{31}$P NMR shifts observed for an intermediate in the formation of 2 by O$\\sb2$ oxidation of 1. The reaction of ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ with O$\\sb2$ has been further investigated to study the conversion of the previously observed intermediate to complex 2. Compound ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ reacted with allyl iodide to form a $\\sigma$-allyl complex, ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9)(\\eta\\sp1$-C$\\sb3$H$\\sb5$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N). This reaction was performed to examine the equilibrium between tridentate trimetaphosphate coordination and bidentate coordination, when both modes are allowed by the 18-electron rule. Finally, a unique reversible conversion of the oxametallacyclobutane complex 2 to the aquo olefin complex ((C$\\sb8$H$\\sb $)Ir(OH$\\sb2)(\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) (3) is reported. The investigation of the interconversion pathway leads to the observation and characterization of two intermediates and offers a clearer view of the mechanism by which complex 2 is formed.","Made available in DSpace on 2014-12-17T21:29:10Z (GMT). No. of bitstreams: 1 9411582.pdf: 3763719 bytes, checksum: 079ba6b198cfa6bc8d7913688f7cc272 (MD5) Previous issue date: 1993","Embargo set by: Seth Robbins for item 72455 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","133 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1993."]},{"key":"dc:title","label":"Title","values":["Studies of the Mechanism of Carbon Oxygen Bond Formation in a Polyoxoanion-Supported Oxairidacyclobutane Complex"]}]}],"canonical_facts":{"dc:contributor":["Klemperer, Walter G."],"dc:creator":["Chen, Jie"],"dc:date":["2014-12-17T21:29:10Z","10000-01-01","1993"],"dc:description":["The goal of this research has been to understand the C-O bond formation mechanism of the oxametallacyclobutane complex, ((C$\\sb8$H$\\sb $O)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (2). The reaction of ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (1) with cyanoolefins was carried out in order to synthesize bidentate (P$\\sb3$O$\\sb9)\\sp{3-}$ complexes, ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp2$O-P$\\sb3$O$\\sb9$)(cyanoolefin)) ((n-$\\rm C\\sb4H\\sb9)\\sb4N\\rbrack\\sb{2}$. The $\\sp{31}$P chemical shifts observed for these complexes were then used to assign the $\\sp{31}$P NMR shifts observed for an intermediate in the formation of 2 by O$\\sb2$ oxidation of 1. The reaction of ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ with O$\\sb2$ has been further investigated to study the conversion of the previously observed intermediate to complex 2. Compound ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ reacted with allyl iodide to form a $\\sigma$-allyl complex, ((C$\\sb8$H$\\sb $)Ir($\\kappa\\sp3$O-P$\\sb3$O$\\sb9)(\\eta\\sp1$-C$\\sb3$H$\\sb5$)) ((n-C$\\sb4$H$\\sb9)\\sb4$N). This reaction was performed to examine the equilibrium between tridentate trimetaphosphate coordination and bidentate coordination, when both modes are allowed by the 18-electron rule. Finally, a unique reversible conversion of the oxametallacyclobutane complex 2 to the aquo olefin complex ((C$\\sb8$H$\\sb $)Ir(OH$\\sb2)(\\kappa\\sp3$O-P$\\sb3$O$\\sb9$)) (3) is reported. The investigation of the interconversion pathway leads to the observation and characterization of two intermediates and offers a clearer view of the mechanism by which complex 2 is formed.","Made available in DSpace on 2014-12-17T21:29:10Z (GMT). No. of bitstreams: 1 9411582.pdf: 3763719 bytes, checksum: 079ba6b198cfa6bc8d7913688f7cc272 (MD5) Previous issue date: 1993","Embargo set by: Seth Robbins for item 72455 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","133 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1993."],"dc:identifier":["http://hdl.handle.net/2142/72287","(UMI)AAI9411582"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Studies of the Mechanism of Carbon Oxygen Bond Formation in a Polyoxoanion-Supported Oxairidacyclobutane Complex"],"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":"2026-07-22T22:26:06Z"}