{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/28703"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/28703","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"The synthesis of sterically demanding ligands and examples of their copper complexes","abstract":"Conditions for promoting the Pd-catalyzed arylation of (N-pyrrolyl)zinc derivatives have been established using aryl bromides, chlorides, and iodides as substrates. In most cases, 0.5 mol% Pd(OAc)₂ can achieve the desired transformation in roughly 24 hours, with the more sterically demanding substrates requiring altered conditions. Typical isolated yields are in excess of 70%. Moreover, methyl- and aryl-substituted pyrrolyl anions have been shown to display similar chemistry using 5.0 mol% Pd(OAc)₂. Though they require longer reaction times, the isolated yields rival those of the unsubstituted analogs. Two new copper(I) N-heterocyclic carbene complexes containing the 2,4,6,2\",4\",6\"-hexaisopropyl-1,1':3',1\"-terphenyl moiety have been synthesized and isolated. The LCuCl complex (92% isolated yield) was made via a one-pot synthesis from the corresponding imidazolinium tetrafluoroborate salt, NaH, and CuCl (L = [1,3-bis-(2,4,6,2\",4\",6\"-hexaisopropyl- [1,1':3',1\"]terphenyl-5'-yl)-4,5-dihydroimidazol-2-ylidene]). The LCuOAc complex (71% isolated yield) was made the same way using CuOAc in place of CuCl.","abstract_html":"Conditions for promoting the Pd-catalyzed arylation of (N-pyrrolyl)zinc derivatives have been established using aryl bromides, chlorides, and iodides as substrates. In most cases, 0.5 mol% Pd(OAc)₂ can achieve the desired transformation in roughly 24 hours, with the more sterically demanding substrates requiring altered conditions. Typical isolated yields are in excess of 70%. Moreover, methyl- and aryl-substituted pyrrolyl anions have been shown to display similar chemistry using 5.0 mol% Pd(OAc)₂. Though they require longer reaction times, the isolated yields rival those of the unsubstituted analogs. Two new copper(I) N-heterocyclic carbene complexes containing the 2,4,6,2",4",6"-hexaisopropyl-1,1':3',1"-terphenyl moiety have been synthesized and isolated. The LCuCl complex (92% isolated yield) was made via a one-pot synthesis from the corresponding imidazolinium tetrafluoroborate salt, NaH, and CuCl (L = [1,3-bis-(2,4,6,2",4",6"-hexaisopropyl- [1,1':3',1"]terphenyl-5'-yl)-4,5-dihydroimidazol-2-ylidene]). The LCuOAc complex (71% isolated yield) was made the same way using CuOAc in place of CuCl.","abstract_has_math":false,"creators":["Rieth, Ryan D., 1978-"],"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":["Joseph Sadighi."],"committee_chairs":[],"committee_members":[],"year":2004,"date_issued":"2004","date_published":"2004","updated_at":"2026-07-22T22:22:30Z","subjects":["Chemistry."],"languages":["en_US"],"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/1721.1/28703","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Joseph Sadighi."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. 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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/1721.1/28703"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004.","Vita.","Includes bibliographical references."]},{"key":"dc:description.abstract","label":"Abstract","values":["Conditions for promoting the Pd-catalyzed arylation of (N-pyrrolyl)zinc derivatives have been established using aryl bromides, chlorides, and iodides as substrates. In most cases, 0.5 mol% Pd(OAc)₂ can achieve the desired transformation in roughly 24 hours, with the more sterically demanding substrates requiring altered conditions. Typical isolated yields are in excess of 70%. Moreover, methyl- and aryl-substituted pyrrolyl anions have been shown to display similar chemistry using 5.0 mol% Pd(OAc)₂. Though they require longer reaction times, the isolated yields rival those of the unsubstituted analogs. Two new copper(I) N-heterocyclic carbene complexes containing the 2,4,6,2\",4\",6\"-hexaisopropyl-1,1':3',1\"-terphenyl moiety have been synthesized and isolated. The LCuCl complex (92% isolated yield) was made via a one-pot synthesis from the corresponding imidazolinium tetrafluoroborate salt, NaH, and CuCl (L = [1,3-bis-(2,4,6,2\",4\",6\"-hexaisopropyl- [1,1':3',1\"]terphenyl-5'-yl)-4,5-dihydroimidazol-2-ylidene]). The LCuOAc complex (71% isolated yield) was made the same way using CuOAc in place of CuCl."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["S.M."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["The synthesis of sterically demanding ligands and examples of their copper complexes"]}]}],"canonical_facts":{"dc:contributor.advisor":["Joseph Sadighi."],"dc:contributor.department":["Massachusetts Institute of Technology. Dept. of Chemistry."],"dc:contributor.other":["Massachusetts Institute of Technology. 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Two new copper(I) N-heterocyclic carbene complexes containing the 2,4,6,2\",4\",6\"-hexaisopropyl-1,1':3',1\"-terphenyl moiety have been synthesized and isolated. The LCuCl complex (92% isolated yield) was made via a one-pot synthesis from the corresponding imidazolinium tetrafluoroborate salt, NaH, and CuCl (L = [1,3-bis-(2,4,6,2\",4\",6\"-hexaisopropyl- [1,1':3',1\"]terphenyl-5'-yl)-4,5-dihydroimidazol-2-ylidene]). The LCuOAc complex (71% isolated yield) was made the same way using CuOAc in place of CuCl."],"dc:description.degree":["S.M."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["http://hdl.handle.net/1721.1/28703"],"dc:language.iso":["en_US"],"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":["The synthesis of sterically demanding ligands and examples of their copper complexes"],"dc:type":["Thesis"]},"updated_at":"2026-07-22T22:22:30Z"}