{"id":{"repo_id":"maryland","oai_identifier":"oai:drum.lib.umd.edu:1903/12863"},"canonical_url":"https://search.dev.ndltd.org/etd/maryland/oai:drum.lib.umd.edu:1903/12863","repository":{"repo_id":"maryland","name":"University of Maryland","base_url":"https://api.drum.lib.umd.edu/server/oai/request"},"display":{"title":"REDUCTIVE ELIMINATION OF (DPMS)PTIV COMPLEXES DERIVED FROM ISOMERIC 2-BUTENEs AND 2-BUTYNE (DPMS=DI(2-PYRIDYL)METHANE SULFONATE)","abstract":"The (dpms)PtII complexes (dpms = di(2-pyridinyl)methanesulfonate)derived from some cyclic olefins can be readily oxidized to PtIV oxetanes, followed by reductive elimination to produce corresponding epoxides. A catalytic version of this reaction can potentially be achieved if decomposition of active species responsible for olefin substitution is avoided. Several attempts were made to solve this problem, and a more hydrophilic analog of the dipyridinemethanesulfonate ligand was obtained. Furthermore, the reductive elimination step of PtIV oxetanes was studied by using diastereomeric cis- and trans-2-butene derivatives. We believe that two mechanisms of C O reductive elimination may be involved in these reactions and that steric repulsion between substituents at the oxetane carbon atoms may play a major role in determining the predominant of the two competing mechanisms. Platinum(IV) η1-butanone complex was synthesized and characterized, which was found to undergo different types of elimination reaction to give a series of butane derivatives as products.","abstract_html":"The (dpms)PtII complexes (dpms = di(2-pyridinyl)methanesulfonate)derived from some cyclic olefins can be readily oxidized to PtIV oxetanes, followed by reductive elimination to produce corresponding epoxides. A catalytic version of this reaction can potentially be achieved if decomposition of active species responsible for olefin substitution is avoided. Several attempts were made to solve this problem, and a more hydrophilic analog of the dipyridinemethanesulfonate ligand was obtained. Furthermore, the reductive elimination step of PtIV oxetanes was studied by using diastereomeric cis- and trans-2-butene derivatives. We believe that two mechanisms of C O reductive elimination may be involved in these reactions and that steric repulsion between substituents at the oxetane carbon atoms may play a major role in determining the predominant of the two competing mechanisms. Platinum(IV) η1-butanone complex was synthesized and characterized, which was found to undergo different types of elimination reaction to give a series of butane derivatives as products.","abstract_has_math":false,"creators":["Liu, Xiaohang"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":"Chemistry","school":null,"contributors":[],"advisors":["Vedernikov, Andrei"],"committee_chairs":[],"committee_members":[],"year":2012,"date_issued":"2012","date_published":"2012","updated_at":"2026-07-24T03:02:17Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/1903/12863","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Vedernikov, Andrei"]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Liu, Xiaohang"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2012-07-14T05:35:04Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2012-07-14T05:35:04Z"]},{"key":"dc:date.issued","label":"Date","values":["2012"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/1903/12863"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The (dpms)PtII complexes (dpms = di(2-pyridinyl)methanesulfonate)derived from some cyclic olefins can be readily oxidized to PtIV oxetanes, followed by reductive elimination to produce corresponding epoxides. A catalytic version of this reaction can potentially be achieved if decomposition of active species responsible for olefin substitution is avoided. Several attempts were made to solve this problem, and a more hydrophilic analog of the dipyridinemethanesulfonate ligand was obtained. Furthermore, the reductive elimination step of PtIV oxetanes was studied by using diastereomeric cis- and trans-2-butene derivatives. We believe that two mechanisms of C O reductive elimination may be involved in these reactions and that steric repulsion between substituents at the oxetane carbon atoms may play a major role in determining the predominant of the two competing mechanisms. Platinum(IV) η1-butanone complex was synthesized and characterized, which was found to undergo different types of elimination reaction to give a series of butane derivatives as products."]},{"key":"dc:title","label":"Title","values":["REDUCTIVE ELIMINATION OF (DPMS)PTIV COMPLEXES DERIVED FROM ISOMERIC 2-BUTENEs AND 2-BUTYNE (DPMS=DI(2-PYRIDYL)METHANE SULFONATE)"]}]}],"canonical_facts":{"dc:contributor.advisor":["Vedernikov, Andrei"],"dc:contributor.department":["Chemistry"],"dc:creator":["Liu, Xiaohang"],"dc:date.accessioned":["2012-07-14T05:35:04Z"],"dc:date.available":["2012-07-14T05:35:04Z"],"dc:date.issued":["2012"],"dc:description.abstract":["The (dpms)PtII complexes (dpms = di(2-pyridinyl)methanesulfonate)derived from some cyclic olefins can be readily oxidized to PtIV oxetanes, followed by reductive elimination to produce corresponding epoxides. A catalytic version of this reaction can potentially be achieved if decomposition of active species responsible for olefin substitution is avoided. Several attempts were made to solve this problem, and a more hydrophilic analog of the dipyridinemethanesulfonate ligand was obtained. Furthermore, the reductive elimination step of PtIV oxetanes was studied by using diastereomeric cis- and trans-2-butene derivatives. We believe that two mechanisms of C O reductive elimination may be involved in these reactions and that steric repulsion between substituents at the oxetane carbon atoms may play a major role in determining the predominant of the two competing mechanisms. Platinum(IV) η1-butanone complex was synthesized and characterized, which was found to undergo different types of elimination reaction to give a series of butane derivatives as products."],"dc:identifier.uri":["http://hdl.handle.net/1903/12863"],"dc:title":["REDUCTIVE ELIMINATION OF (DPMS)PTIV COMPLEXES DERIVED FROM ISOMERIC 2-BUTENEs AND 2-BUTYNE (DPMS=DI(2-PYRIDYL)METHANE SULFONATE)"],"dc:type":["Thesis"]},"updated_at":"2026-07-24T03:02:17Z"}