{"id":{"repo_id":"ohiolink","oai_identifier":"oai:etd.ohiolink.edu:toledo1363282845"},"canonical_url":"https://search.dev.ndltd.org/etd/ohiolink/oai:etd.ohiolink.edu:toledo1363282845","repository":{"repo_id":"ohiolink","name":"OhioLINK","base_url":"https://etd.ohiolink.edu/acprod/odb_etd/ws/oai/oai"},"display":{"title":"Synthesis of Early Transition Metal Complexes Supported by Pyrrolyl and Indolyl Based Ligands","abstract":"High oxidation state early transition metal complexes are Lewis acidic and electrophilic. The electrophilic center promotes the coordination and insertion of electron-rich substrates; such as alkenes, alkynes, and epoxides. Anionic ligands enable the metal center to retain Lewis acidity for catalytic applications and chelating ligands increase stability due to the chelate effect. Frequently, Constrained Geometry Catalysts (CGC) are comprised of early transition metals supported by chelating ligands. The chelating CGC ligands usually contain an η5-dienyl moiety tethered to anionic donor. The pendent donor conventionally is an amide or alkoxide derivative which in turn quenches some of the Lewis acidity of the transition metal through E-M π-donation (E = O, N) of lone pair electrons. Substituting heterocyclic nitrogen moiety (pyrrole or indole) for the pendent donor will reduce the N-M π-donation due to lone pair delocalization within the aromatic ring. This thesis reports further developments of the cyclopentadienyl derivative of constrained geometry ligands featuring indolyl- and pyrrolyl- donor moieties and indolyl- and pyrrolyl- supported group 5 imido complexes.In chapter 2, the synthesis and characterization of a series of dipyrrolyl- and diindolylmethane precursors envisioned to produce the Cp-based trianionic ligand are reported. Three new methanes are described, 5-(chloromethyl)dipyrrolylmethane, 2,2’-di(5-mesityl-1H-pyrrol-2-yl) ethyl chloride, and ethyl 2-(2,2’-di-3-methylindolyl)propionate, along with attempts to react with sodium cyclopentadienyl. In additional, tetramethylcyclopentadienyl acetaldehyde diethyl acetyl was synthesized and reactivity with pyrrole and 3-methylindole is discussed. Chapter 3 reports synthesis and characterization of a series of elementary Group 5 imido complexes supported by pyrrolyl- and indolyl- ligands. A total of six compounds were synthesized by amine elimination and characterization included 1H and 13C NMR spectroscopy. The structure of (tBuN)Nb{di(3-methylindolyl)phenylmethane}(NEt2)(NHEt2) was further characterized by X-ray crystallography to confirm connectivity. These complexes are envisioned to have broad application to catalytic processes.","abstract_html":"High oxidation state early transition metal complexes are Lewis acidic and electrophilic. The electrophilic center promotes the coordination and insertion of electron-rich substrates; such as alkenes, alkynes, and epoxides. Anionic ligands enable the metal center to retain Lewis acidity for catalytic applications and chelating ligands increase stability due to the chelate effect. Frequently, Constrained Geometry Catalysts (CGC) are comprised of early transition metals supported by chelating ligands. The chelating CGC ligands usually contain an η5-dienyl moiety tethered to anionic donor. The pendent donor conventionally is an amide or alkoxide derivative which in turn quenches some of the Lewis acidity of the transition metal through E-M π-donation (E = O, N) of lone pair electrons. Substituting heterocyclic nitrogen moiety (pyrrole or indole) for the pendent donor will reduce the N-M π-donation due to lone pair delocalization within the aromatic ring. This thesis reports further developments of the cyclopentadienyl derivative of constrained geometry ligands featuring indolyl- and pyrrolyl- donor moieties and indolyl- and pyrrolyl- supported group 5 imido complexes.In chapter 2, the synthesis and characterization of a series of dipyrrolyl- and diindolylmethane precursors envisioned to produce the Cp-based trianionic ligand are reported. Three new methanes are described, 5-(chloromethyl)dipyrrolylmethane, 2,2’-di(5-mesityl-1H-pyrrol-2-yl) ethyl chloride, and ethyl 2-(2,2’-di-3-methylindolyl)propionate, along with attempts to react with sodium cyclopentadienyl. In additional, tetramethylcyclopentadienyl acetaldehyde diethyl acetyl was synthesized and reactivity with pyrrole and 3-methylindole is discussed. Chapter 3 reports synthesis and characterization of a series of elementary Group 5 imido complexes supported by pyrrolyl- and indolyl- ligands. A total of six compounds were synthesized by amine elimination and characterization included 1H and 13C NMR spectroscopy. The structure of (tBuN)Nb{di(3-methylindolyl)phenylmethane}(NEt2)(NHEt2) was further characterized by X-ray crystallography to confirm connectivity. These complexes are envisioned to have broad application to catalytic processes.","abstract_has_math":false,"creators":["Yeisley, Christopher R."],"institution":"University of Toledo","degree_name":"Master of Science","degree_level":"masters","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Mason, Mark"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2013,"date_issued":"2013-06-14","date_published":"2013-06-14","updated_at":"2026-07-24T03:36:39Z","subjects":["Chemistry","CGCs","Group 5 imido","trianionic","indole","pyrrole"],"languages":["English"],"rights":["unrestricted","This thesis or dissertation is protected by copyright: some rights reserved. It is licensed for use under a Creative Commons license. Specific terms and permissions are available from this document's record in the OhioLINK ETD Center."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://rave.ohiolink.edu/etdc/view?acc_num=toledo1363282845","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Mason, Mark"]},{"key":"dc:creator","label":"Author","values":["Yeisley, Christopher R."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2013-06-14"]},{"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","CGCs","Group 5 imido","trianionic","indole","pyrrole"]}]},{"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: some rights reserved. It is licensed for use under a Creative Commons license. Specific terms and permissions are available from this document's record in the OhioLINK ETD Center."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://rave.ohiolink.edu/etdc/view?acc_num=toledo1363282845"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["High oxidation state early transition metal complexes are Lewis acidic and electrophilic. The electrophilic center promotes the coordination and insertion of electron-rich substrates; such as alkenes, alkynes, and epoxides. Anionic ligands enable the metal center to retain Lewis acidity for catalytic applications and chelating ligands increase stability due to the chelate effect. Frequently, Constrained Geometry Catalysts (CGC) are comprised of early transition metals supported by chelating ligands. The chelating CGC ligands usually contain an η5-dienyl moiety tethered to anionic donor. The pendent donor conventionally is an amide or alkoxide derivative which in turn quenches some of the Lewis acidity of the transition metal through E-M π-donation (E = O, N) of lone pair electrons. Substituting heterocyclic nitrogen moiety (pyrrole or indole) for the pendent donor will reduce the N-M π-donation due to lone pair delocalization within the aromatic ring. This thesis reports further developments of the cyclopentadienyl derivative of constrained geometry ligands featuring indolyl- and pyrrolyl- donor moieties and indolyl- and pyrrolyl- supported group 5 imido complexes.In chapter 2, the synthesis and characterization of a series of dipyrrolyl- and diindolylmethane precursors envisioned to produce the Cp-based trianionic ligand are reported. Three new methanes are described, 5-(chloromethyl)dipyrrolylmethane, 2,2’-di(5-mesityl-1H-pyrrol-2-yl) ethyl chloride, and ethyl 2-(2,2’-di-3-methylindolyl)propionate, along with attempts to react with sodium cyclopentadienyl. In additional, tetramethylcyclopentadienyl acetaldehyde diethyl acetyl was synthesized and reactivity with pyrrole and 3-methylindole is discussed. Chapter 3 reports synthesis and characterization of a series of elementary Group 5 imido complexes supported by pyrrolyl- and indolyl- ligands. A total of six compounds were synthesized by amine elimination and characterization included 1H and 13C NMR spectroscopy. The structure of (tBuN)Nb{di(3-methylindolyl)phenylmethane}(NEt2)(NHEt2) was further characterized by X-ray crystallography to confirm connectivity. These complexes are envisioned to have broad application to catalytic processes."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf","p.79","2.27 MB"]},{"key":"dc:title","label":"Title","values":["Synthesis of Early Transition Metal Complexes Supported by Pyrrolyl and Indolyl Based Ligands"]}]}],"canonical_facts":{"dc:contributor":["Mason, Mark"],"dc:creator":["Yeisley, Christopher R."],"dc:date":["2013-06-14"],"dc:description":["High oxidation state early transition metal complexes are Lewis acidic and electrophilic. The electrophilic center promotes the coordination and insertion of electron-rich substrates; such as alkenes, alkynes, and epoxides. Anionic ligands enable the metal center to retain Lewis acidity for catalytic applications and chelating ligands increase stability due to the chelate effect. Frequently, Constrained Geometry Catalysts (CGC) are comprised of early transition metals supported by chelating ligands. The chelating CGC ligands usually contain an η5-dienyl moiety tethered to anionic donor. The pendent donor conventionally is an amide or alkoxide derivative which in turn quenches some of the Lewis acidity of the transition metal through E-M π-donation (E = O, N) of lone pair electrons. Substituting heterocyclic nitrogen moiety (pyrrole or indole) for the pendent donor will reduce the N-M π-donation due to lone pair delocalization within the aromatic ring. This thesis reports further developments of the cyclopentadienyl derivative of constrained geometry ligands featuring indolyl- and pyrrolyl- donor moieties and indolyl- and pyrrolyl- supported group 5 imido complexes.In chapter 2, the synthesis and characterization of a series of dipyrrolyl- and diindolylmethane precursors envisioned to produce the Cp-based trianionic ligand are reported. Three new methanes are described, 5-(chloromethyl)dipyrrolylmethane, 2,2’-di(5-mesityl-1H-pyrrol-2-yl) ethyl chloride, and ethyl 2-(2,2’-di-3-methylindolyl)propionate, along with attempts to react with sodium cyclopentadienyl. In additional, tetramethylcyclopentadienyl acetaldehyde diethyl acetyl was synthesized and reactivity with pyrrole and 3-methylindole is discussed. Chapter 3 reports synthesis and characterization of a series of elementary Group 5 imido complexes supported by pyrrolyl- and indolyl- ligands. A total of six compounds were synthesized by amine elimination and characterization included 1H and 13C NMR spectroscopy. The structure of (tBuN)Nb{di(3-methylindolyl)phenylmethane}(NEt2)(NHEt2) was further characterized by X-ray crystallography to confirm connectivity. These complexes are envisioned to have broad application to catalytic processes."],"dc:format":["application/pdf","p.79","2.27 MB"],"dc:identifier":["http://rave.ohiolink.edu/etdc/view?acc_num=toledo1363282845"],"dc:language":["English"],"dc:publisher":["University of Toledo / OhioLINK"],"dc:rights":["unrestricted","This thesis or dissertation is protected by copyright: some rights reserved. It is licensed for use under a Creative Commons license. Specific terms and permissions are available from this document's record in the OhioLINK ETD Center."],"dc:subject":["Chemistry","CGCs","Group 5 imido","trianionic","indole","pyrrole"],"dc:title":["Synthesis of Early Transition Metal Complexes Supported by Pyrrolyl and Indolyl Based Ligands"],"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":"2026-07-24T03:36:39Z"}