{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/73438"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/73438","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Novel reactions of a neutral organic reductant : reductive coupling and nanoparticle synthesis","abstract":"A recently developed bis-pyridinylidene neutral organic electron donor captured our interest as a potential source of new chemistries for reductive coupling and the synthesis of group IV nanoparticles. This super electron donor was used as a co-reductant for nickel-catalyzed reductive coupling of aryl halides in order for the reaction to be homogeneous and avoid the traditional co-reductant, zinc, previously reported for these Yamamoto-type dehalogenative couplings. Reductive coupling was somewhat successful for specific substrates, including 4- bromoanisole and 2,5-dibromothiophene, but competing hydrodehalogenation of the aryl halide was problematic for both expanding the substrate scope and increasing the length of the polymers generated from this reaction. The attempt to synthesize silicon and germanium nanoparticles from reduction of the corresponding tetrachloride precursors using this super organic electron donor met limited success. Dimerization of silicon species occurred, but there was little conclusive evidence of nanoparticle formation. Finally, in a brief side-project to explore other applications of the organic reductant, the molecule was shown to successfully n-dope both p-type and n-type organic electronic materials.","abstract_html":"A recently developed bis-pyridinylidene neutral organic electron donor captured our interest as a potential source of new chemistries for reductive coupling and the synthesis of group IV nanoparticles. This super electron donor was used as a co-reductant for nickel-catalyzed reductive coupling of aryl halides in order for the reaction to be homogeneous and avoid the traditional co-reductant, zinc, previously reported for these Yamamoto-type dehalogenative couplings. Reductive coupling was somewhat successful for specific substrates, including 4- bromoanisole and 2,5-dibromothiophene, but competing hydrodehalogenation of the aryl halide was problematic for both expanding the substrate scope and increasing the length of the polymers generated from this reaction. The attempt to synthesize silicon and germanium nanoparticles from reduction of the corresponding tetrachloride precursors using this super organic electron donor met limited success. Dimerization of silicon species occurred, but there was little conclusive evidence of nanoparticle formation. Finally, in a brief side-project to explore other applications of the organic reductant, the molecule was shown to successfully n-dope both p-type and n-type organic electronic materials.","abstract_has_math":false,"creators":["Mork, Anna Jolene"],"institution":"Massachusetts Institute of Technology","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Dept. of Chemistry.","school":null,"contributors":[],"advisors":["Timothy M. Swager."],"committee_chairs":[],"committee_members":[],"year":2012,"date_issued":"2012","date_published":"2012","updated_at":"2026-07-22T22:22:30Z","subjects":["Chemistry."],"languages":["eng"],"rights":["M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission."],"rights_urls":["http://dspace.mit.edu/handle/1721.1/7582"],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/1721.1/73438","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Timothy M. Swager."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. Dept. of Chemistry."]},{"key":"dc:contributor.other","label":"Dc Contributor Other","values":["Massachusetts Institute of Technology. Dept. of Chemistry."]},{"key":"dc:creator","label":"Author","values":["Mork, Anna Jolene"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2012-09-27T18:12:05Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2012-09-27T18:12:05Z"]},{"key":"dc:date.issued","label":"Date","values":["2012"]},{"key":"dc:publisher","label":"Institution","values":["Massachusetts Institute of Technology"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"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":["M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about 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":["http://hdl.handle.net/1721.1/73438"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2012.","Vita. Cataloged from PDF version of thesis.","Includes bibliographical references (p. 53-55)."]},{"key":"dc:description.abstract","label":"Abstract","values":["A recently developed bis-pyridinylidene neutral organic electron donor captured our interest as a potential source of new chemistries for reductive coupling and the synthesis of group IV nanoparticles. This super electron donor was used as a co-reductant for nickel-catalyzed reductive coupling of aryl halides in order for the reaction to be homogeneous and avoid the traditional co-reductant, zinc, previously reported for these Yamamoto-type dehalogenative couplings. Reductive coupling was somewhat successful for specific substrates, including 4- bromoanisole and 2,5-dibromothiophene, but competing hydrodehalogenation of the aryl halide was problematic for both expanding the substrate scope and increasing the length of the polymers generated from this reaction. The attempt to synthesize silicon and germanium nanoparticles from reduction of the corresponding tetrachloride precursors using this super organic electron donor met limited success. Dimerization of silicon species occurred, but there was little conclusive evidence of nanoparticle formation. Finally, in a brief side-project to explore other applications of the organic reductant, the molecule was shown to successfully n-dope both p-type and n-type organic electronic materials."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["S.M."]},{"key":"dc:title","label":"Title","values":["Novel reactions of a neutral organic reductant : reductive coupling and nanoparticle synthesis"]}]}],"canonical_facts":{"dc:contributor.advisor":["Timothy M. Swager."],"dc:contributor.department":["Massachusetts Institute of Technology. Dept. of Chemistry."],"dc:contributor.other":["Massachusetts Institute of Technology. Dept. of Chemistry."],"dc:creator":["Mork, Anna Jolene"],"dc:date.accessioned":["2012-09-27T18:12:05Z"],"dc:date.available":["2012-09-27T18:12:05Z"],"dc:date.issued":["2012"],"dc:description":["Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2012.","Vita. Cataloged from PDF version of thesis.","Includes bibliographical references (p. 53-55)."],"dc:description.abstract":["A recently developed bis-pyridinylidene neutral organic electron donor captured our interest as a potential source of new chemistries for reductive coupling and the synthesis of group IV nanoparticles. This super electron donor was used as a co-reductant for nickel-catalyzed reductive coupling of aryl halides in order for the reaction to be homogeneous and avoid the traditional co-reductant, zinc, previously reported for these Yamamoto-type dehalogenative couplings. Reductive coupling was somewhat successful for specific substrates, including 4- bromoanisole and 2,5-dibromothiophene, but competing hydrodehalogenation of the aryl halide was problematic for both expanding the substrate scope and increasing the length of the polymers generated from this reaction. The attempt to synthesize silicon and germanium nanoparticles from reduction of the corresponding tetrachloride precursors using this super organic electron donor met limited success. Dimerization of silicon species occurred, but there was little conclusive evidence of nanoparticle formation. Finally, in a brief side-project to explore other applications of the organic reductant, the molecule was shown to successfully n-dope both p-type and n-type organic electronic materials."],"dc:description.degree":["S.M."],"dc:identifier.uri":["http://hdl.handle.net/1721.1/73438"],"dc:language.iso":["eng"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission."],"dc:rights.uri":["http://dspace.mit.edu/handle/1721.1/7582"],"dc:subject":["Chemistry."],"dc:title":["Novel reactions of a neutral organic reductant : reductive coupling and nanoparticle synthesis"],"dc:type":["Thesis"]},"updated_at":"2026-07-22T22:22:30Z"}