{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/138166"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/138166","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"Sharing the Burden of Reactivity: Synthesis, Characterization, and Reactivity of Phosphino-Alkoxide First-Row Transition Metal Complexes","abstract":"Bond activation is both central in many reaction mechanisms and essential to industrial production of chemicals. Many industries, such as pharmaceutical and petrochemical production, use precious metals to perform critical synthetic transformations that rely on bond activation. Due to the scarce nature of these precious metals, alternative approaches to bond activation have been sought. One such alternative approach is the polarization of covalent bonds of the substrate with earth-abundant catalysts. Through careful control of the ligand environment and metal selection, specific substrates can be targeted with precision. This dissertation describes the synthesis of complexes featuring earth-abundant 3d transition metals in monometallic complexes, bimetallic complexes, and frustrated Lewis pairs. Specifically, a phosphino-alkoxide ligand was developed to promote high-spin complex formation, produce unconventional geometries, and enable controlled dimerization. The complexes produced with this ligand were screened for bond activation capabilities, revealing activity for alkyne cyclotrimerization with certain monometallic complexes, both individually and in pairs. Overall, this work demonstrates the promise of earth-abundant 3d transition metal complexes as alternatives to precious metal catalysts for bond activation.","abstract_html":"Bond activation is both central in many reaction mechanisms and essential to industrial production of chemicals. Many industries, such as pharmaceutical and petrochemical production, use precious metals to perform critical synthetic transformations that rely on bond activation. Due to the scarce nature of these precious metals, alternative approaches to bond activation have been sought. One such alternative approach is the polarization of covalent bonds of the substrate with earth-abundant catalysts. Through careful control of the ligand environment and metal selection, specific substrates can be targeted with precision. This dissertation describes the synthesis of complexes featuring earth-abundant 3d transition metals in monometallic complexes, bimetallic complexes, and frustrated Lewis pairs. Specifically, a phosphino-alkoxide ligand was developed to promote high-spin complex formation, produce unconventional geometries, and enable controlled dimerization. The complexes produced with this ligand were screened for bond activation capabilities, revealing activity for alkyne cyclotrimerization with certain monometallic complexes, both individually and in pairs. Overall, this work demonstrates the promise of earth-abundant 3d transition metal complexes as alternatives to precious metal catalysts for bond activation.","abstract_has_math":false,"creators":["Williams, Matthew Jacob"],"institution":"Virginia Tech","degree_name":"Doctor of Philosophy","degree_level":"doctoral","degree_discipline":"Chemistry","degree_department":"Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":["Schulz, Michael","Merola, Joseph S."],"committee_members":["Deck, Paul A.","Morris, Amanda"],"year":2025,"date_issued":"2025-10-13","date_published":"2025-10-13","updated_at":"2026-07-22T22:19:29Z","subjects":["First-row transition metal complexes","alkoxide complexes","bimetallic complexes","unsaturated carbon-carbon bond cyclotrimerization"],"languages":["en"],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["vt_gsexam:44683"],"render_values":[{"text":"vt_gsexam:44683","href":null,"code":true}]}]},"links":{"outbound_url":"https://hdl.handle.net/10919/138166","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.committeechair","label":"Committee Chair","values":["Schulz, Michael","Merola, Joseph S."]},{"key":"dc:contributor.committeemember","label":"Committee Member","values":["Deck, Paul A.","Morris, Amanda"]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Williams, Matthew Jacob"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2025-10-14T08:00:27Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2025-10-14T08:00:27Z"]},{"key":"dc:date.issued","label":"Date","values":["2025-10-13"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Tech"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Virginia Polytechnic Institute and State University"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["First-row transition metal complexes","alkoxide complexes","bimetallic complexes","unsaturated carbon-carbon bond cyclotrimerization"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["In Copyright"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/vocab/InC/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["vt_gsexam:44683"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/10919/138166"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Bond activation is both central in many reaction mechanisms and essential to industrial production of chemicals. Many industries, such as pharmaceutical and petrochemical production, use precious metals to perform critical synthetic transformations that rely on bond activation. Due to the scarce nature of these precious metals, alternative approaches to bond activation have been sought. One such alternative approach is the polarization of covalent bonds of the substrate with earth-abundant catalysts. Through careful control of the ligand environment and metal selection, specific substrates can be targeted with precision. This dissertation describes the synthesis of complexes featuring earth-abundant 3d transition metals in monometallic complexes, bimetallic complexes, and frustrated Lewis pairs. Specifically, a phosphino-alkoxide ligand was developed to promote high-spin complex formation, produce unconventional geometries, and enable controlled dimerization. The complexes produced with this ligand were screened for bond activation capabilities, revealing activity for alkyne cyclotrimerization with certain monometallic complexes, both individually and in pairs. Overall, this work demonstrates the promise of earth-abundant 3d transition metal complexes as alternatives to precious metal catalysts for bond activation."]},{"key":"dc:description.abstractgeneral","label":"General Abstract","values":["Breaking and forming chemical bonds is a key component of producing many products, from pharmaceuticals to petrochemicals. Today, these industries often rely on rare and expensive metals to carry out these important chemical transformations. Because these metals are scarce and costly, more sustainable alternatives are being explored. This dissertation describes the synthesis of complexes featuring earth-abundant metals. These complexes were evaluated for their ability to facilitate complicated chemical transformations. Specifically, certain complexes demonstrated the ability to produce sophisticated molecules with potential applications in pharmaceuticals and organic electronics. Overall, this work demonstrates the promise of earth-abundant metal complexes as alternatives to precious metal-based processes."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Doctor of Philosophy"]},{"key":"dc:format.medium","label":"Dc Format Medium","values":["ETD"]},{"key":"dc:title","label":"Title","values":["Sharing the Burden of Reactivity: Synthesis, Characterization, and Reactivity of Phosphino-Alkoxide First-Row Transition Metal Complexes"]}]}],"canonical_facts":{"dc:contributor.committeechair":["Schulz, Michael","Merola, Joseph S."],"dc:contributor.committeemember":["Deck, Paul A.","Morris, Amanda"],"dc:contributor.department":["Chemistry"],"dc:creator":["Williams, Matthew Jacob"],"dc:date.accessioned":["2025-10-14T08:00:27Z"],"dc:date.available":["2025-10-14T08:00:27Z"],"dc:date.issued":["2025-10-13"],"dc:description.abstract":["Bond activation is both central in many reaction mechanisms and essential to industrial production of chemicals. Many industries, such as pharmaceutical and petrochemical production, use precious metals to perform critical synthetic transformations that rely on bond activation. Due to the scarce nature of these precious metals, alternative approaches to bond activation have been sought. One such alternative approach is the polarization of covalent bonds of the substrate with earth-abundant catalysts. Through careful control of the ligand environment and metal selection, specific substrates can be targeted with precision. This dissertation describes the synthesis of complexes featuring earth-abundant 3d transition metals in monometallic complexes, bimetallic complexes, and frustrated Lewis pairs. Specifically, a phosphino-alkoxide ligand was developed to promote high-spin complex formation, produce unconventional geometries, and enable controlled dimerization. The complexes produced with this ligand were screened for bond activation capabilities, revealing activity for alkyne cyclotrimerization with certain monometallic complexes, both individually and in pairs. Overall, this work demonstrates the promise of earth-abundant 3d transition metal complexes as alternatives to precious metal catalysts for bond activation."],"dc:description.abstractgeneral":["Breaking and forming chemical bonds is a key component of producing many products, from pharmaceuticals to petrochemicals. Today, these industries often rely on rare and expensive metals to carry out these important chemical transformations. Because these metals are scarce and costly, more sustainable alternatives are being explored. This dissertation describes the synthesis of complexes featuring earth-abundant metals. These complexes were evaluated for their ability to facilitate complicated chemical transformations. Specifically, certain complexes demonstrated the ability to produce sophisticated molecules with potential applications in pharmaceuticals and organic electronics. Overall, this work demonstrates the promise of earth-abundant metal complexes as alternatives to precious metal-based processes."],"dc:description.degree":["Doctor of Philosophy"],"dc:format.medium":["ETD"],"dc:identifier.other":["vt_gsexam:44683"],"dc:identifier.uri":["https://hdl.handle.net/10919/138166"],"dc:language.iso":["en"],"dc:publisher":["Virginia Tech"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:subject":["First-row transition metal complexes","alkoxide complexes","bimetallic complexes","unsaturated carbon-carbon bond cyclotrimerization"],"dc:title":["Sharing the Burden of Reactivity: Synthesis, Characterization, and Reactivity of Phosphino-Alkoxide First-Row Transition Metal Complexes"],"dc:type":["Dissertation"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Doctor of Philosophy"],"thesis:institution_name":["Virginia Polytechnic Institute and State University"]},"updated_at":"2026-07-22T22:19:29Z"}