{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/124054"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/124054","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Oxygen atom transfer with manganese-exchanged metal-organic frameworks","abstract":"Oxygenates represent some of the most versatile commodity chemicals, justifying continued interest in the discovery of new selective oxidation catalysts from both a fundamental and applied perspective. Metal-organic frameworks (MOFs) are an attractive platform for catalysis because they enable access to unique coordination environments and reactivities; this is due in part to their tunability combined with the site isolation offered by their solid state. In one example, partial substitution of Zn[superscript II] by Mn[superscript II] in Zn₄O(terephthalate)₃ (MOF-5) leads to a distorted all-oxygen ligand field supporting a single Mn[superscript II] site, whose structure was confirmed by Mn K-edge X-ray absorption spectroscopy. Upon exposure to [superscript t]BuSO₂PhIO, Mn-MOF-5 produces a putative Mn[superscript IV]-oxo intermediate, which upon further reaction with adventitious hydrogen is trapped as a Mn[superscript III]-OH species.","abstract_html":"Oxygenates represent some of the most versatile commodity chemicals, justifying continued interest in the discovery of new selective oxidation catalysts from both a fundamental and applied perspective. Metal-organic frameworks (MOFs) are an attractive platform for catalysis because they enable access to unique coordination environments and reactivities; this is due in part to their tunability combined with the site isolation offered by their solid state. In one example, partial substitution of Zn[superscript II] by Mn[superscript II] in Zn₄O(terephthalate)₃ (MOF-5) leads to a distorted all-oxygen ligand field supporting a single Mn[superscript II] site, whose structure was confirmed by Mn K-edge X-ray absorption spectroscopy. Upon exposure to [superscript t]BuSO₂PhIO, Mn-MOF-5 produces a putative Mn[superscript IV]-oxo intermediate, which upon further reaction with adventitious hydrogen is trapped as a Mn[superscript III]-OH species.","abstract_has_math":false,"creators":["Stubbs, Amanda Walcott."],"institution":"Massachusetts Institute of Technology","degree_name":"Doctoral","degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Department of Chemistry","school":null,"contributors":[],"advisors":["Mircea Dincă."],"committee_chairs":[],"committee_members":[],"year":2019,"date_issued":"2019","date_published":"2019","updated_at":"2026-07-22T22:22:27Z","subjects":["Chemistry."],"languages":["eng"],"rights":["MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission."],"rights_urls":["http://dspace.mit.edu/handle/1721.1/7582"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1721.1/124054","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Mircea Dincă."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. Department of Chemistry","Chem"]},{"key":"dc:contributor.other","label":"Dc Contributor Other","values":["Massachusetts Institute of Technology. Department of Chemistry."]},{"key":"dc:creator","label":"Author","values":["Stubbs, Amanda Walcott."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2020-03-09T18:51:20Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2020-03-09T18:51:20Z"]},{"key":"dc:date.issued","label":"Date","values":["2019"]},{"key":"dc:publisher","label":"Institution","values":["Massachusetts Institute of Technology"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctoral"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry."]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission."]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://dspace.mit.edu/handle/1721.1/7582"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/1721.1/124054"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2019","\"September 2019.\" Cataloged from PDF version of thesis.","Includes bibliographical references (pages 93-105)."]},{"key":"dc:description.abstract","label":"Abstract","values":["Oxygenates represent some of the most versatile commodity chemicals, justifying continued interest in the discovery of new selective oxidation catalysts from both a fundamental and applied perspective. Metal-organic frameworks (MOFs) are an attractive platform for catalysis because they enable access to unique coordination environments and reactivities; this is due in part to their tunability combined with the site isolation offered by their solid state. In one example, partial substitution of Zn[superscript II] by Mn[superscript II] in Zn₄O(terephthalate)₃ (MOF-5) leads to a distorted all-oxygen ligand field supporting a single Mn[superscript II] site, whose structure was confirmed by Mn K-edge X-ray absorption spectroscopy. Upon exposure to [superscript t]BuSO₂PhIO, Mn-MOF-5 produces a putative Mn[superscript IV]-oxo intermediate, which upon further reaction with adventitious hydrogen is trapped as a Mn[superscript III]-OH species.","Most intriguingly, the intermediacy of the high-spin Mn[superscript IV]-oxo species is likely responsible for catalytic activity of the Mn[superscript II]-MOF-5 precatalyst, which in the presence of [superscript t]BuSO₂PhIO catalyzes oxygen atom transfer reactivity to selectively form epoxides from cyclic alkenes. In a second study, partial substitution of Zn[superscript II] by Mn[superscript II] in Zn₅(OAc)₄(bibenzotriazolate)₃ (CFA-1) yields a material in which manganese is supported by a ligand environment reminiscent of that found in molecular scorpionates. Unlike molecular analogs, Mn-CFA-1 is capable of activating molecular oxygen to convert substrates with sufficiently weak C-H bonds, such as cyclohexene, to alcohol and ketone products. In-situ spectroscopies including Mn K-edge X-ray absorption, DRIFTS, and Diffuse Reflectance UV-vis indicate that reactivity proceeds through a high valent Mn-peroxo species.","These results demonstrate that MOF secondary building units serve as competent platforms for accessing high-valent metal-oxygen species that consequently engage in catalytic oxygen atom transfer chemistry owing to the ligand fields and site isolation provided by the material."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph. D."]},{"key":"dc:title","label":"Title","values":["Oxygen atom transfer with manganese-exchanged metal-organic frameworks"]}]}],"canonical_facts":{"dc:contributor.advisor":["Mircea Dincă."],"dc:contributor.department":["Massachusetts Institute of Technology. Department of Chemistry","Chem"],"dc:contributor.other":["Massachusetts Institute of Technology. Department of Chemistry."],"dc:creator":["Stubbs, Amanda Walcott."],"dc:date.accessioned":["2020-03-09T18:51:20Z"],"dc:date.available":["2020-03-09T18:51:20Z"],"dc:date.issued":["2019"],"dc:description":["Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2019","\"September 2019.\" Cataloged from PDF version of thesis.","Includes bibliographical references (pages 93-105)."],"dc:description.abstract":["Oxygenates represent some of the most versatile commodity chemicals, justifying continued interest in the discovery of new selective oxidation catalysts from both a fundamental and applied perspective. Metal-organic frameworks (MOFs) are an attractive platform for catalysis because they enable access to unique coordination environments and reactivities; this is due in part to their tunability combined with the site isolation offered by their solid state. In one example, partial substitution of Zn[superscript II] by Mn[superscript II] in Zn₄O(terephthalate)₃ (MOF-5) leads to a distorted all-oxygen ligand field supporting a single Mn[superscript II] site, whose structure was confirmed by Mn K-edge X-ray absorption spectroscopy. Upon exposure to [superscript t]BuSO₂PhIO, Mn-MOF-5 produces a putative Mn[superscript IV]-oxo intermediate, which upon further reaction with adventitious hydrogen is trapped as a Mn[superscript III]-OH species.","Most intriguingly, the intermediacy of the high-spin Mn[superscript IV]-oxo species is likely responsible for catalytic activity of the Mn[superscript II]-MOF-5 precatalyst, which in the presence of [superscript t]BuSO₂PhIO catalyzes oxygen atom transfer reactivity to selectively form epoxides from cyclic alkenes. In a second study, partial substitution of Zn[superscript II] by Mn[superscript II] in Zn₅(OAc)₄(bibenzotriazolate)₃ (CFA-1) yields a material in which manganese is supported by a ligand environment reminiscent of that found in molecular scorpionates. Unlike molecular analogs, Mn-CFA-1 is capable of activating molecular oxygen to convert substrates with sufficiently weak C-H bonds, such as cyclohexene, to alcohol and ketone products. In-situ spectroscopies including Mn K-edge X-ray absorption, DRIFTS, and Diffuse Reflectance UV-vis indicate that reactivity proceeds through a high valent Mn-peroxo species.","These results demonstrate that MOF secondary building units serve as competent platforms for accessing high-valent metal-oxygen species that consequently engage in catalytic oxygen atom transfer chemistry owing to the ligand fields and site isolation provided by the material."],"dc:description.degree":["Ph. D."],"dc:identifier.uri":["https://hdl.handle.net/1721.1/124054"],"dc:language.iso":["eng"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission."],"dc:rights.uri":["http://dspace.mit.edu/handle/1721.1/7582"],"dc:subject":["Chemistry."],"dc:title":["Oxygen atom transfer with manganese-exchanged metal-organic frameworks"],"dc:type":["Thesis"],"thesis:degree_name":["Doctoral"]},"updated_at":"2026-07-22T22:22:27Z"}