{"id":{"repo_id":"missouri","oai_identifier":"oai:mospace.umsystem.edu:10355/14503"},"canonical_url":"https://search.dev.ndltd.org/etd/missouri/oai:mospace.umsystem.edu:10355/14503","repository":{"repo_id":"missouri","name":"University of Missouri","base_url":"https://mospace.umsystem.edu/oai/request"},"display":{"title":"Alkene oxidation by platinum (II) oxo/hydroxo complexes","abstract":"The facile reaction between tetranuclear Pt-oxo complex [(COD)4Pt4([mu]2-O)2Cl2]2[BF4]2 (1) and norbornene (NB) yields the stable platinaoxetane [(COD)2Pt2(OC7H10)Cl][BF4] (2) in quantitative yield. A rapid reaction between NB and the novel (1,5-COD)Pt(II)-hydroxo complex [(COD)2Pt(OH)2]2+ (4) is observed and the protonated platinaoxetane [(COD)Pt(OH)C7H10)]+ (5) is formed in quantitative yield. Both Pt-hydroxo complex 4 and protonated platinaoxetane 5 are found to be important species in the formation of platinaoxetane 2. Mechanisms for formation of platinaoxetanes 2 and 5 are proposed. Pt-hydroxo complex 4 reacts readily with ethylene, propylene and 1-butene. All three reactions, resembling Wacker chemistry, yield alkene oxidation products: acetaldehyde, acetone and ethyl-­‐methyl ketone, respectively. Pt-ethyl alkyl complexes are yielded as the only Pt containing complexes. A proposed mechanism for these alkene oxidations is described. Pt-hydroxo complex 4 also reacts with cyclohexene. In this case the reaction takes an allylic C-H activation pathway to produce the cyclohexyl allyl complex [(COD)Pt(C6H9)]+ (55).","abstract_html":"The facile reaction between tetranuclear Pt-oxo complex [(COD)4Pt4([mu]2-O)2Cl2]2[BF4]2 (1) and norbornene (NB) yields the stable platinaoxetane [(COD)2Pt2(OC7H10)Cl][BF4] (2) in quantitative yield. A rapid reaction between NB and the novel (1,5-COD)Pt(II)-hydroxo complex [(COD)2Pt(OH)2]2+ (4) is observed and the protonated platinaoxetane [(COD)Pt(OH)C7H10)]+ (5) is formed in quantitative yield. Both Pt-hydroxo complex 4 and protonated platinaoxetane 5 are found to be important species in the formation of platinaoxetane 2. Mechanisms for formation of platinaoxetanes 2 and 5 are proposed. Pt-hydroxo complex 4 reacts readily with ethylene, propylene and 1-butene. All three reactions, resembling Wacker chemistry, yield alkene oxidation products: acetaldehyde, acetone and ethyl-­‐methyl ketone, respectively. Pt-ethyl alkyl complexes are yielded as the only Pt containing complexes. A proposed mechanism for these alkene oxidations is described. Pt-hydroxo complex 4 also reacts with cyclohexene. In this case the reaction takes an allylic C-H activation pathway to produce the cyclohexyl allyl complex [(COD)Pt(C6H9)]+ (55).","abstract_has_math":false,"creators":["Weliange, Nandita Malathi"],"institution":"University of Missouri--Columbia","degree_name":"Ph. D.","degree_level":"Doctoral","degree_discipline":"Chemistry (MU)","degree_department":null,"school":null,"contributors":[],"advisors":["Sharp, Paul Ray"],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011","date_published":"2011","updated_at":"2026-07-24T03:08:09Z","subjects":["platinaoxetane","quantitative yield","alkene oxidation products"],"languages":["eng","English"],"rights":["OpenAccess."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.32469/10355/14503"],"render_values":[{"text":"https://doi.org/10.32469/10355/14503","href":"https://doi.org/10.32469/10355/14503","code":true}]}]},"links":{"outbound_url":"https://hdl.handle.net/10355/14503","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Sharp, Paul Ray"]},{"key":"dc:creator","label":"Author","values":["Weliange, Nandita Malathi"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2012-06-05T13:03:22Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2012-12-16T12:15:08Z"]},{"key":"dc:date.issued","label":"Date","values":["2011"]},{"key":"dc:publisher","label":"Institution","values":["University of Missouri--Columbia"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry (MU)"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph. 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Sharp","Vita.","Ph. D. University of Missouri--Columbia 2011.","\"December 2011\""]},{"key":"dc:description.abstract","label":"Abstract","values":["The facile reaction between tetranuclear Pt-oxo complex [(COD)4Pt4([mu]2-O)2Cl2]2[BF4]2 (1) and norbornene (NB) yields the stable platinaoxetane [(COD)2Pt2(OC7H10)Cl][BF4] (2) in quantitative yield. A rapid reaction between NB and the novel (1,5-COD)Pt(II)-hydroxo complex [(COD)2Pt(OH)2]2+ (4) is observed and the protonated platinaoxetane [(COD)Pt(OH)C7H10)]+ (5) is formed in quantitative yield. Both Pt-hydroxo complex 4 and protonated platinaoxetane 5 are found to be important species in the formation of platinaoxetane 2. Mechanisms for formation of platinaoxetanes 2 and 5 are proposed. Pt-hydroxo complex 4 reacts readily with ethylene, propylene and 1-butene. All three reactions, resembling Wacker chemistry, yield alkene oxidation products: acetaldehyde, acetone and ethyl-­‐methyl ketone, respectively. Pt-ethyl alkyl complexes are yielded as the only Pt containing complexes. A proposed mechanism for these alkene oxidations is described. Pt-hydroxo complex 4 also reacts with cyclohexene. In this case the reaction takes an allylic C-H activation pathway to produce the cyclohexyl allyl complex [(COD)Pt(C6H9)]+ (55)."]},{"key":"dc:title","label":"Title","values":["Alkene oxidation by platinum (II) oxo/hydroxo complexes"]}]}],"canonical_facts":{"dc:contributor.advisor":["Sharp, Paul Ray"],"dc:creator":["Weliange, Nandita Malathi"],"dc:date.accessioned":["2012-06-05T13:03:22Z"],"dc:date.available":["2012-12-16T12:15:08Z"],"dc:date.issued":["2011"],"dc:description":["Title from PDF of title page (University of Missouri--Columbia, viewed on June 5, 2012).","The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file.","Dissertation advisor: Dr. Paul R. Sharp","Vita.","Ph. D. University of Missouri--Columbia 2011.","\"December 2011\""],"dc:description.abstract":["The facile reaction between tetranuclear Pt-oxo complex [(COD)4Pt4([mu]2-O)2Cl2]2[BF4]2 (1) and norbornene (NB) yields the stable platinaoxetane [(COD)2Pt2(OC7H10)Cl][BF4] (2) in quantitative yield. A rapid reaction between NB and the novel (1,5-COD)Pt(II)-hydroxo complex [(COD)2Pt(OH)2]2+ (4) is observed and the protonated platinaoxetane [(COD)Pt(OH)C7H10)]+ (5) is formed in quantitative yield. Both Pt-hydroxo complex 4 and protonated platinaoxetane 5 are found to be important species in the formation of platinaoxetane 2. Mechanisms for formation of platinaoxetanes 2 and 5 are proposed. Pt-hydroxo complex 4 reacts readily with ethylene, propylene and 1-butene. All three reactions, resembling Wacker chemistry, yield alkene oxidation products: acetaldehyde, acetone and ethyl-­‐methyl ketone, respectively. Pt-ethyl alkyl complexes are yielded as the only Pt containing complexes. A proposed mechanism for these alkene oxidations is described. Pt-hydroxo complex 4 also reacts with cyclohexene. In this case the reaction takes an allylic C-H activation pathway to produce the cyclohexyl allyl complex [(COD)Pt(C6H9)]+ (55)."],"dc:identifier.doi":["https://doi.org/10.32469/10355/14503"],"dc:identifier.uri":["https://hdl.handle.net/10355/14503"],"dc:language":["English"],"dc:language.iso":["eng"],"dc:publisher":["University of Missouri--Columbia"],"dc:rights":["OpenAccess."],"dc:subject":["platinaoxetane","quantitative yield","alkene oxidation products"],"dc:title":["Alkene oxidation by platinum (II) oxo/hydroxo complexes"],"dc:type":["Thesis"],"thesis:degree_discipline":["Chemistry (MU)"],"thesis:degree_level":["Doctoral"],"thesis:degree_name":["Ph. D."],"thesis:institution_name":["University of Missouri--Columbia"]},"updated_at":"2026-07-24T03:08:09Z"}