{"id":{"repo_id":"oklahoma-thes","oai_identifier":"oai:shareok.org:11244/5968"},"canonical_url":"https://search.dev.ndltd.org/etd/oklahoma-thes/oai:shareok.org:11244/5968","repository":{"repo_id":"oklahoma-thes","name":"University of Oklahoma","base_url":"https://shareok.org/server/oai/request"},"display":{"title":"Investigation of ligand misdirection using the kinetic element effect and the kinetic enthalpy effect.","abstract":"Metal complexes were synthesized with the atropisomeric dabp. X-ray crystal structures were solved for [Ru(bipy)2(dabp)]2+ and [(eta6-C6H6)Ru(dabp)(Cl)]+. Only one diastereomer was observed for [Ru(bipy)2(dabp)] 2+ in the 1H NMR spectrum. Exchange was observed and measured for the ruthenium and osmium complexes of [(eta6-C 6H6)M(dabp)(Cl)]+.","abstract_html":"Metal complexes were synthesized with the atropisomeric dabp. X-ray crystal structures were solved for [Ru(bipy)2(dabp)]2+ and [(eta6-C6H6)Ru(dabp)(Cl)]+. Only one diastereomer was observed for [Ru(bipy)2(dabp)] 2+ in the 1H NMR spectrum. Exchange was observed and measured for the ruthenium and osmium complexes of [(eta6-C 6H6)M(dabp)(Cl)]+.","abstract_has_math":false,"creators":["Alguindigue, Susan Stanislav."],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Ashby, Michael T.,"],"committee_chairs":[],"committee_members":[],"year":2000,"date_issued":"2000","date_published":"2000","updated_at":"2026-08-21T16:47:16Z","subjects":["Molecular orbitals.","Ligand binding (Biochemistry) g","Crystal field theory.","Chemistry, Inorganic."],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/11244/5968","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"source_record":{"url":"https://shareok.org/server/oai/request?verb=GetRecord&metadataPrefix=dim&identifier=oai%3Ashareok.org%3A11244%2F5968","prefix":"dim"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Ashby, Michael T.,"]},{"key":"dc:creator","label":"Author","values":["Alguindigue, Susan Stanislav."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2013-08-16T12:30:55Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2013-08-16T12:30:55Z"]},{"key":"dc:date.issued","label":"Date","values":["2000"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Molecular orbitals.","Ligand binding (Biochemistry) g","Crystal field theory.","Chemistry, Inorganic."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/11244/5968"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Metal complexes were synthesized with the atropisomeric dabp. X-ray crystal structures were solved for [Ru(bipy)2(dabp)]2+ and [(eta6-C6H6)Ru(dabp)(Cl)]+. Only one diastereomer was observed for [Ru(bipy)2(dabp)] 2+ in the 1H NMR spectrum. Exchange was observed and measured for the ruthenium and osmium complexes of [(eta6-C 6H6)M(dabp)(Cl)]+.","[M(bipy)2(1,1'-biiq)]2+, [(eta6-C6H6)M(1,1'-biiq)(Cl)] +, [(eta6-C6H6)M(1,1 '-biiq)(I)]+ and [(eta6-C 6H6)M(dabp)(Cl)]+ (M = Ru, Os) are the only examples in the literature of third-row transition metal complexes having faster rates of atropisomerization than their second-row congegers. While the KEE varies among the 1,1'-biiq compounds, the KHE is nearly the same for each system. KHE may be a better indicator of the misdirected metal-ligand bond.","A comparison of the rates of isomerization of the ruthenium and osmium derivatives of [M(bipy)2(1,1'-biiq)] 2+, [(eta6-C6H6)M(1,1 '-biiq), [(eta6-C6H6)M(1,1 '-biiq)(I)]+, and [(eta6-C 6H6)M(dabp)(Cl)]+ has led to the introduction of the term Kinetic Element Effect (KEE). The KEE is the ratio of the rates of isomerization reactions of second-row and third-row metal-ligand complexes (KEE = k2nd/k3rd). A Kinetic Enthalpy Effect (KHE) can be defined as the ratio of enthalpy of activation for the third row and second-row atropisomerization reactions (KHE = DeltaH‡ 3rd /DeltaH‡ 2nd).","[(eta6-C6H6)M(1,1' -biiq)(X)]+ (M = Ru, Os; X = Cl, I) were synthesized. 1H NMR chemical shifts were assigned by 2D-COSY experiments. Exchange between enantiomers was observed by 2D-EXSY experiments. Rates of atropisomerization of the 1,1'-biiq ligand were measured for all four derivatives by NMR. Rates were found to be faster for the ruthenium derivatives than the osmium derivatives.","A series of Cp2Zr(Cl)(SR) (R = Methyl, ethyl, iso -propyl, tert-butyl) have been synthesized. The ground-state conformation that is adopted by these d0 metal compounds represent a compromise between stabilizing Mdpi-Sppi interactions and destabilizing R-Cp steric contact. The thiolate ligands in such complexes are therefore misdirected. Rotational barriers (DeltaG‡ ) about the Zr-S bond have been measured by 1H NMR for the first time. For (R = Methyl, ethyl, and iso-propyl, the barriers are proportional to the steric demand of the ligand and the bond strength of the metal-sulfur bond. A much lower barrier was measured for R = tert-butyl. (Abstract shortened by UMI.)"]},{"key":"dc:title","label":"Title","values":["Investigation of ligand misdirection using the kinetic element effect and the kinetic enthalpy effect."]}]}],"canonical_facts":{"dc:contributor.advisor":["Ashby, Michael T.,"],"dc:creator":["Alguindigue, Susan Stanislav."],"dc:date.accessioned":["2013-08-16T12:30:55Z"],"dc:date.available":["2013-08-16T12:30:55Z"],"dc:date.issued":["2000"],"dc:description.abstract":["Metal complexes were synthesized with the atropisomeric dabp. X-ray crystal structures were solved for [Ru(bipy)2(dabp)]2+ and [(eta6-C6H6)Ru(dabp)(Cl)]+. Only one diastereomer was observed for [Ru(bipy)2(dabp)] 2+ in the 1H NMR spectrum. Exchange was observed and measured for the ruthenium and osmium complexes of [(eta6-C 6H6)M(dabp)(Cl)]+.","[M(bipy)2(1,1'-biiq)]2+, [(eta6-C6H6)M(1,1'-biiq)(Cl)] +, [(eta6-C6H6)M(1,1 '-biiq)(I)]+ and [(eta6-C 6H6)M(dabp)(Cl)]+ (M = Ru, Os) are the only examples in the literature of third-row transition metal complexes having faster rates of atropisomerization than their second-row congegers. While the KEE varies among the 1,1'-biiq compounds, the KHE is nearly the same for each system. KHE may be a better indicator of the misdirected metal-ligand bond.","A comparison of the rates of isomerization of the ruthenium and osmium derivatives of [M(bipy)2(1,1'-biiq)] 2+, [(eta6-C6H6)M(1,1 '-biiq), [(eta6-C6H6)M(1,1 '-biiq)(I)]+, and [(eta6-C 6H6)M(dabp)(Cl)]+ has led to the introduction of the term Kinetic Element Effect (KEE). The KEE is the ratio of the rates of isomerization reactions of second-row and third-row metal-ligand complexes (KEE = k2nd/k3rd). A Kinetic Enthalpy Effect (KHE) can be defined as the ratio of enthalpy of activation for the third row and second-row atropisomerization reactions (KHE = DeltaH‡ 3rd /DeltaH‡ 2nd).","[(eta6-C6H6)M(1,1' -biiq)(X)]+ (M = Ru, Os; X = Cl, I) were synthesized. 1H NMR chemical shifts were assigned by 2D-COSY experiments. Exchange between enantiomers was observed by 2D-EXSY experiments. Rates of atropisomerization of the 1,1'-biiq ligand were measured for all four derivatives by NMR. Rates were found to be faster for the ruthenium derivatives than the osmium derivatives.","A series of Cp2Zr(Cl)(SR) (R = Methyl, ethyl, iso -propyl, tert-butyl) have been synthesized. The ground-state conformation that is adopted by these d0 metal compounds represent a compromise between stabilizing Mdpi-Sppi interactions and destabilizing R-Cp steric contact. The thiolate ligands in such complexes are therefore misdirected. Rotational barriers (DeltaG‡ ) about the Zr-S bond have been measured by 1H NMR for the first time. For (R = Methyl, ethyl, and iso-propyl, the barriers are proportional to the steric demand of the ligand and the bond strength of the metal-sulfur bond. A much lower barrier was measured for R = tert-butyl. (Abstract shortened by UMI.)"],"dc:identifier.uri":["http://hdl.handle.net/11244/5968"],"dc:subject":["Molecular orbitals.","Ligand binding (Biochemistry) g","Crystal field theory.","Chemistry, Inorganic."],"dc:title":["Investigation of ligand misdirection using the kinetic element effect and the kinetic enthalpy effect."],"dc:type":["Thesis"]},"updated_at":"2026-08-21T16:47:16Z"}