{"id":{"repo_id":"ohiolink","oai_identifier":"oai:etd.ohiolink.edu:toledo1356544579"},"canonical_url":"https://search.dev.ndltd.org/etd/ohiolink/oai:etd.ohiolink.edu:toledo1356544579","repository":{"repo_id":"ohiolink","name":"OhioLINK","base_url":"https://etd.ohiolink.edu/acprod/odb_etd/ws/oai/oai"},"display":{"title":"Investigation of the Steric and Electronic Properties of 3-Iminophosphine Ligands in Chelated Palladium Allyl Complexes for Use in the Regioselective Hydroamination of Allenes","abstract":"A series of (3-iminophosphine)allylpalladium triflate complexes varying in both steric and electronic features was isolated and characterized. The propensity of the complexes in this series to regioselectively catalyze the hydroamination of 3-methyl-1,2-butadiene with aryl amines to form solely the kinetic product at room temperature was studied by observing conversion to products via NMR spectroscopy. An understanding of the importance of these 3-iminophosphine ligand features guides the rational design of future catalysts. The 3-iminophosphine ligand composed of di-tert-butyl phosphine, cyclobutene backbone, and tert-butyl imine provided the most active palladium catalyst for this hydroamination when compared to the other complexes in the collection. Larger alicyclic backbone sizes decrease catalytic activity, as does steric hindrance at the imine substituent group. Tertiary aliphatic groups on the phosphorus are necessary for effective catalysis, as primary and secondary aliphatics and aromatic groups also decrease the catalytic activity. Highly basic imine moieties were also shown to decrease catalytic activity.","abstract_html":"A series of (3-iminophosphine)allylpalladium triflate complexes varying in both steric and electronic features was isolated and characterized. The propensity of the complexes in this series to regioselectively catalyze the hydroamination of 3-methyl-1,2-butadiene with aryl amines to form solely the kinetic product at room temperature was studied by observing conversion to products via NMR spectroscopy. An understanding of the importance of these 3-iminophosphine ligand features guides the rational design of future catalysts. The 3-iminophosphine ligand composed of di-tert-butyl phosphine, cyclobutene backbone, and tert-butyl imine provided the most active palladium catalyst for this hydroamination when compared to the other complexes in the collection. Larger alicyclic backbone sizes decrease catalytic activity, as does steric hindrance at the imine substituent group. Tertiary aliphatic groups on the phosphorus are necessary for effective catalysis, as primary and secondary aliphatics and aromatic groups also decrease the catalytic activity. Highly basic imine moieties were also shown to decrease catalytic activity.","abstract_has_math":false,"creators":["Zingales, Nicholas C."],"institution":"University of Toledo","degree_name":"Master of Science","degree_level":"masters","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Schmidt, Joseph"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2013,"date_issued":"2013-08-22","date_published":"2013-08-22","updated_at":"2026-07-24T03:36:23Z","subjects":["Chemistry","hydroamination","3-iminophosphine","palladium","intermolecular, anilines","allenes"],"languages":["English"],"rights":["unrestricted","This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://rave.ohiolink.edu/etdc/view?acc_num=toledo1356544579","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Schmidt, Joseph"]},{"key":"dc:creator","label":"Author","values":["Zingales, Nicholas C."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2013-08-22"]},{"key":"dc:publisher","label":"Institution","values":["University of Toledo / OhioLINK"]},{"key":"dc:type","label":"Dc Type","values":["Electronic Thesis or Dissertation"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["masters"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Science"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Toledo"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry","hydroamination","3-iminophosphine","palladium","intermolecular, anilines","allenes"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English"]},{"key":"dc:rights","label":"Dc Rights","values":["unrestricted","This thesis or dissertation is protected by copyright: all rights reserved. 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The 3-iminophosphine ligand composed of di-tert-butyl phosphine, cyclobutene backbone, and tert-butyl imine provided the most active palladium catalyst for this hydroamination when compared to the other complexes in the collection. Larger alicyclic backbone sizes decrease catalytic activity, as does steric hindrance at the imine substituent group. Tertiary aliphatic groups on the phosphorus are necessary for effective catalysis, as primary and secondary aliphatics and aromatic groups also decrease the catalytic activity. Highly basic imine moieties were also shown to decrease catalytic activity."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf","p.82","1.43 MB"]},{"key":"dc:title","label":"Title","values":["Investigation of the Steric and Electronic Properties of 3-Iminophosphine Ligands in Chelated Palladium Allyl Complexes for Use in the Regioselective Hydroamination of Allenes"]}]}],"canonical_facts":{"dc:contributor":["Schmidt, Joseph"],"dc:creator":["Zingales, Nicholas C."],"dc:date":["2013-08-22"],"dc:description":["A series of (3-iminophosphine)allylpalladium triflate complexes varying in both steric and electronic features was isolated and characterized. The propensity of the complexes in this series to regioselectively catalyze the hydroamination of 3-methyl-1,2-butadiene with aryl amines to form solely the kinetic product at room temperature was studied by observing conversion to products via NMR spectroscopy. An understanding of the importance of these 3-iminophosphine ligand features guides the rational design of future catalysts. The 3-iminophosphine ligand composed of di-tert-butyl phosphine, cyclobutene backbone, and tert-butyl imine provided the most active palladium catalyst for this hydroamination when compared to the other complexes in the collection. Larger alicyclic backbone sizes decrease catalytic activity, as does steric hindrance at the imine substituent group. Tertiary aliphatic groups on the phosphorus are necessary for effective catalysis, as primary and secondary aliphatics and aromatic groups also decrease the catalytic activity. Highly basic imine moieties were also shown to decrease catalytic activity."],"dc:format":["application/pdf","p.82","1.43 MB"],"dc:identifier":["http://rave.ohiolink.edu/etdc/view?acc_num=toledo1356544579"],"dc:language":["English"],"dc:publisher":["University of Toledo / OhioLINK"],"dc:rights":["unrestricted","This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws."],"dc:subject":["Chemistry","hydroamination","3-iminophosphine","palladium","intermolecular, anilines","allenes"],"dc:title":["Investigation of the Steric and Electronic Properties of 3-Iminophosphine Ligands in Chelated Palladium Allyl Complexes for Use in the Regioselective Hydroamination of Allenes"],"dc:type":["Electronic Thesis or Dissertation"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["masters"],"thesis:degree_name":["Master of Science"],"thesis:institution_name":["University of Toledo"]},"updated_at":"2026-07-24T03:36:23Z"}