{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84418"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84418","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"New Materials Based on Metallodithiolenes, Fullerenes, and Cyclopentadienyl Iron Complexes","abstract":"We focused on the development of methods to functionalize a metal cluster through cyclopentadienyl (Cp) ligands. The cluster, $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4,$ is prepared from the thermolysis of xylene solutions of $\\rm Cp\\sb2Fe\\sb2(CO)\\sb4$ and PPh$\\sb3$ to yield primarily $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ together with smaller amounts of $\\rm(C\\sb5H\\sb4Ph)CP\\sb3Fe\\sb4(CO)\\sb4$ and $\\rm Cp\\sb3Fe\\sb3(CO)\\sb3(PPh\\sb2).$ Cluster, $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4,$ can be alkylated and arylated using organolithium reagents to give the derivatives $\\rm(C\\sb5H\\sb4R)Cp\\sb3Fe\\sb4(CO)\\sb4.$ This reaction is competitive with reduction of $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ by the organolithium reagent. A more versatile method for functionalizing $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ involves its deprotonation using lithium diisopropyl amide (LDA) followed by treatment with electrophiles to give $\\rm(C\\sb5H\\sb4X)Cp\\sb3Fe\\sb4(CO)\\sb4\\ (X=C(OH)HCH\\sb3,\\ CO\\sb2H,\\ CHO,\\ SPh,\\ PPh\\sb2).$ Excess of LDA gave increased amounts of the di- and even trifunctionalized derivatives $\\rm(C\\sb5H\\sb4X)\\sb{x}Cp\\sb{4-x}Fe\\sb4(CO)\\sb4$ (x = 2, 3). The reactivity of the lithiated clusters towards organic electrophiles led us to investigate routes to dicubane clusters. Treatment of $\\rm(C\\sb5H\\sb4CHO)Cp\\sb3Fe\\sb4(CO)\\sb4$ with the lithiated cluster gave the dicluster $\\rm\\lbrack(C\\sb5H\\sb4)Cp\\sb3Fe\\sb4(CO)\\sb4\\rbrack\\sb2CHOH.$ The use of the cluster as a ligand was demonstrated by the synthesis of the adducts $\\rm(C\\sb5H\\sb4PPh\\sb2ML\\sb{n})Cp\\sb3Fe\\sb4(CO)\\sb4,$ where ML$\\rm\\sb{n}$ = RuCl$\\sb2$(cymene), IrCl(1,5-$\\rm C\\sb8H\\sb{12}).$ Single crystal X-ray diffraction was employed to characterize $\\rm\\lbrack(C\\sb5H\\sb4)Cp\\sb3Fe\\sb4(CO)\\sb4\\rbrack\\sb2CHOH$ and $\\rm(C\\sb3H\\sb4PPh\\sb2)Cp\\sb3Fe\\sb4(CO)\\sb4RuCl\\sb2(cymene).$.","abstract_html":"We focused on the development of methods to functionalize a metal cluster through cyclopentadienyl (Cp) ligands. The cluster, $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4,$ is prepared from the thermolysis of xylene solutions of $\\rm Cp\\sb2Fe\\sb2(CO)\\sb4$ and PPh$\\sb3$ to yield primarily $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ together with smaller amounts of $\\rm(C\\sb5H\\sb4Ph)CP\\sb3Fe\\sb4(CO)\\sb4$ and $\\rm Cp\\sb3Fe\\sb3(CO)\\sb3(PPh\\sb2).$ Cluster, $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4,$ can be alkylated and arylated using organolithium reagents to give the derivatives $\\rm(C\\sb5H\\sb4R)Cp\\sb3Fe\\sb4(CO)\\sb4.$ This reaction is competitive with reduction of $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ by the organolithium reagent. A more versatile method for functionalizing $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ involves its deprotonation using lithium diisopropyl amide (LDA) followed by treatment with electrophiles to give <span class=\"etd-inline-math\">\\rm(C\\sb5H\\sb4X)Cp\\sb3Fe\\sb4(CO)\\sb4 (X=C(OH)HCH\\sb3, CO\\sb2H, CHO, SPh, PPh\\sb2).</span> Excess of LDA gave increased amounts of the di- and even trifunctionalized derivatives $\\rm(C\\sb5H\\sb4X)\\sb{x}Cp\\sb{4-x}Fe\\sb4(CO)\\sb4$ (x = 2, 3). The reactivity of the lithiated clusters towards organic electrophiles led us to investigate routes to dicubane clusters. Treatment of $\\rm(C\\sb5H\\sb4CHO)Cp\\sb3Fe\\sb4(CO)\\sb4$ with the lithiated cluster gave the dicluster $\\rm\\lbrack(C\\sb5H\\sb4)Cp\\sb3Fe\\sb4(CO)\\sb4\\rbrack\\sb2CHOH.$ The use of the cluster as a ligand was demonstrated by the synthesis of the adducts $\\rm(C\\sb5H\\sb4PPh\\sb2ML\\sb{n})Cp\\sb3Fe\\sb4(CO)\\sb4,$ where ML$\\rm\\sb{n}$ = RuCl$\\sb2$(cymene), IrCl(1,5-$\\rm C\\sb8H\\sb{12}).$ Single crystal X-ray diffraction was employed to characterize $\\rm\\lbrack(C\\sb5H\\sb4)Cp\\sb3Fe\\sb4(CO)\\sb4\\rbrack\\sb2CHOH$ and $\\rm(C\\sb3H\\sb4PPh\\sb2)Cp\\sb3Fe\\sb4(CO)\\sb4RuCl\\sb2(cymene).$.","abstract_has_math":true,"creators":["Westmeyer, Mark David"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Rauchfuss, Thomas B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:14:23Z","date_published":"2015-09-25T22:14:23Z","updated_at":"2026-07-22T22:26:23Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI9904620"],"render_values":[{"text":"(MiAaPQ)AAI9904620","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84418","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Rauchfuss, Thomas B."]},{"key":"dc:creator","label":"Author","values":["Westmeyer, Mark David"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:14:23Z","10000-01-01","1998"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Inorganic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/84418","(MiAaPQ)AAI9904620"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["We focused on the development of methods to functionalize a metal cluster through cyclopentadienyl (Cp) ligands. The cluster, $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4,$ is prepared from the thermolysis of xylene solutions of $\\rm Cp\\sb2Fe\\sb2(CO)\\sb4$ and PPh$\\sb3$ to yield primarily $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ together with smaller amounts of $\\rm(C\\sb5H\\sb4Ph)CP\\sb3Fe\\sb4(CO)\\sb4$ and $\\rm Cp\\sb3Fe\\sb3(CO)\\sb3(PPh\\sb2).$ Cluster, $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4,$ can be alkylated and arylated using organolithium reagents to give the derivatives $\\rm(C\\sb5H\\sb4R)Cp\\sb3Fe\\sb4(CO)\\sb4.$ This reaction is competitive with reduction of $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ by the organolithium reagent. A more versatile method for functionalizing $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ involves its deprotonation using lithium diisopropyl amide (LDA) followed by treatment with electrophiles to give $\\rm(C\\sb5H\\sb4X)Cp\\sb3Fe\\sb4(CO)\\sb4\\ (X=C(OH)HCH\\sb3,\\ CO\\sb2H,\\ CHO,\\ SPh,\\ PPh\\sb2).$ Excess of LDA gave increased amounts of the di- and even trifunctionalized derivatives $\\rm(C\\sb5H\\sb4X)\\sb{x}Cp\\sb{4-x}Fe\\sb4(CO)\\sb4$ (x = 2, 3). The reactivity of the lithiated clusters towards organic electrophiles led us to investigate routes to dicubane clusters. Treatment of $\\rm(C\\sb5H\\sb4CHO)Cp\\sb3Fe\\sb4(CO)\\sb4$ with the lithiated cluster gave the dicluster $\\rm\\lbrack(C\\sb5H\\sb4)Cp\\sb3Fe\\sb4(CO)\\sb4\\rbrack\\sb2CHOH.$ The use of the cluster as a ligand was demonstrated by the synthesis of the adducts $\\rm(C\\sb5H\\sb4PPh\\sb2ML\\sb{n})Cp\\sb3Fe\\sb4(CO)\\sb4,$ where ML$\\rm\\sb{n}$ = RuCl$\\sb2$(cymene), IrCl(1,5-$\\rm C\\sb8H\\sb{12}).$ Single crystal X-ray diffraction was employed to characterize $\\rm\\lbrack(C\\sb5H\\sb4)Cp\\sb3Fe\\sb4(CO)\\sb4\\rbrack\\sb2CHOH$ and $\\rm(C\\sb3H\\sb4PPh\\sb2)Cp\\sb3Fe\\sb4(CO)\\sb4RuCl\\sb2(cymene).$.","Made available in DSpace on 2015-09-25T22:14:23Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9904620.pdf: 6956908 bytes, checksum: 17682aff251384a789f84f757ba2b459 (MD5) Previous issue date: 1998","Embargo set by: Seth Robbins for item 85699 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","168 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1998."]},{"key":"dc:title","label":"Title","values":["New Materials Based on Metallodithiolenes, Fullerenes, and Cyclopentadienyl Iron Complexes"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Westmeyer, Mark David"],"dc:date":["2015-09-25T22:14:23Z","10000-01-01","1998"],"dc:description":["We focused on the development of methods to functionalize a metal cluster through cyclopentadienyl (Cp) ligands. The cluster, $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4,$ is prepared from the thermolysis of xylene solutions of $\\rm Cp\\sb2Fe\\sb2(CO)\\sb4$ and PPh$\\sb3$ to yield primarily $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ together with smaller amounts of $\\rm(C\\sb5H\\sb4Ph)CP\\sb3Fe\\sb4(CO)\\sb4$ and $\\rm Cp\\sb3Fe\\sb3(CO)\\sb3(PPh\\sb2).$ Cluster, $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4,$ can be alkylated and arylated using organolithium reagents to give the derivatives $\\rm(C\\sb5H\\sb4R)Cp\\sb3Fe\\sb4(CO)\\sb4.$ This reaction is competitive with reduction of $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ by the organolithium reagent. A more versatile method for functionalizing $\\rm Cp\\sb4Fe\\sb4(CO)\\sb4$ involves its deprotonation using lithium diisopropyl amide (LDA) followed by treatment with electrophiles to give $\\rm(C\\sb5H\\sb4X)Cp\\sb3Fe\\sb4(CO)\\sb4\\ (X=C(OH)HCH\\sb3,\\ CO\\sb2H,\\ CHO,\\ SPh,\\ PPh\\sb2).$ Excess of LDA gave increased amounts of the di- and even trifunctionalized derivatives $\\rm(C\\sb5H\\sb4X)\\sb{x}Cp\\sb{4-x}Fe\\sb4(CO)\\sb4$ (x = 2, 3). The reactivity of the lithiated clusters towards organic electrophiles led us to investigate routes to dicubane clusters. Treatment of $\\rm(C\\sb5H\\sb4CHO)Cp\\sb3Fe\\sb4(CO)\\sb4$ with the lithiated cluster gave the dicluster $\\rm\\lbrack(C\\sb5H\\sb4)Cp\\sb3Fe\\sb4(CO)\\sb4\\rbrack\\sb2CHOH.$ The use of the cluster as a ligand was demonstrated by the synthesis of the adducts $\\rm(C\\sb5H\\sb4PPh\\sb2ML\\sb{n})Cp\\sb3Fe\\sb4(CO)\\sb4,$ where ML$\\rm\\sb{n}$ = RuCl$\\sb2$(cymene), IrCl(1,5-$\\rm C\\sb8H\\sb{12}).$ Single crystal X-ray diffraction was employed to characterize $\\rm\\lbrack(C\\sb5H\\sb4)Cp\\sb3Fe\\sb4(CO)\\sb4\\rbrack\\sb2CHOH$ and $\\rm(C\\sb3H\\sb4PPh\\sb2)Cp\\sb3Fe\\sb4(CO)\\sb4RuCl\\sb2(cymene).$.","Made available in DSpace on 2015-09-25T22:14:23Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9904620.pdf: 6956908 bytes, checksum: 17682aff251384a789f84f757ba2b459 (MD5) Previous issue date: 1998","Embargo set by: Seth Robbins for item 85699 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","168 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1998."],"dc:identifier":["http://hdl.handle.net/2142/84418","(MiAaPQ)AAI9904620"],"dc:language":["eng"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["New Materials Based on Metallodithiolenes, Fullerenes, and Cyclopentadienyl Iron Complexes"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:26:23Z"}