{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21829"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21829","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"High oxidation state organometallics and their charge transfer materials","abstract":"This research has been directed toward the systematic design and synthesis of highly oxidizing complexes. These complexes have been used as components in the molecular synthesis of solid state materials displaying cooperative electronic interactions. Complexes of the type CpVX$\\sb3$ (Cp = $\\eta\\sp5$-C$\\rm\\sb5$H$\\sb5$ or -$\\rm C\\sb5H\\sb4$Me; X = Cl, Br) are highly oxidizing. The oxidation potential can be tuned by changes in the cyclopentadienyl ligand, halides, or with a strongly $\\pi$-bonding oxide. Their electronic ground states were characterized.","abstract_html":"This research has been directed toward the systematic design and synthesis of highly oxidizing complexes. These complexes have been used as components in the molecular synthesis of solid state materials displaying cooperative electronic interactions. Complexes of the type CpVX$\\sb3$ (Cp = $\\eta\\sp5$-C$\\rm\\sb5$H$\\sb5$ or -$\\rm C\\sb5H\\sb4$Me; X = Cl, Br) are highly oxidizing. The oxidation potential can be tuned by changes in the cyclopentadienyl ligand, halides, or with a strongly <span class=\"etd-inline-math\">&pi;</span>-bonding oxide. Their electronic ground states were characterized.","abstract_has_math":true,"creators":["Morse, David B."],"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":2011,"date_issued":"2011-05-07T13:20:24Z","date_published":"2011-05-07T13:20:24Z","updated_at":"2026-07-22T22:25:18Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1989 Morse, David B."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI8924907","(UMI)AAI8924907"],"render_values":[{"text":"AAI8924907","href":null,"code":true},{"text":"(UMI)AAI8924907","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21829","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":["Morse, David B."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:20:24Z","10000-01-01","1989"]},{"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"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1989 Morse, David B."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI8924907","(UMI)AAI8924907","http://hdl.handle.net/2142/21829"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["This research has been directed toward the systematic design and synthesis of highly oxidizing complexes. These complexes have been used as components in the molecular synthesis of solid state materials displaying cooperative electronic interactions. Complexes of the type CpVX$\\sb3$ (Cp = $\\eta\\sp5$-C$\\rm\\sb5$H$\\sb5$ or -$\\rm C\\sb5H\\sb4$Me; X = Cl, Br) are highly oxidizing. The oxidation potential can be tuned by changes in the cyclopentadienyl ligand, halides, or with a strongly $\\pi$-bonding oxide. Their electronic ground states were characterized.","Reaction of these organometallic acceptors with the organic donor TmTEF (E = S, Se; tetramethyltetrathio(seleno)fulvalene) formed materials such as (TmTTF) ((MeCp)VCl$\\sb3\\rbrack$ and (TmTTF$\\rbrack\\sb3\\lbrack\\{$MeCp) VCl$\\sb2\\}\\sb2$O$\\rbrack\\sb2$. The mixed-valence salt of TmTTF and $\\{$(MeCp)VCl$\\sb2\\}\\sb2$O$\\sp-$ exhibits field dependent magnetic behavior. The single crystal magnetic susceptibility of this one-dimensional solid has defined it as an XY ferromagnet. The low field ferromagnetic response arises from spin alignment within the organometallic fragments. The complex (TmTSF) (CpVBr$\\sb3\\rbrack\\cdot$CH$\\sb2$Cl$\\sb2$ also displays field dependent properties.","Oxidants such as CpVX$\\sb3$ also form partial charge transfer complexes. The organometallic donor Cp$\\sb2$Fe forms a complex with CpVBr$\\sb3$, which exists as Cp$\\sb2$Fe$\\sp+$CpVBr$\\sb3$- in the solid state. CpVI$\\sb3$ forms a charge transfer aggregate in solution wherein one group acts as a donor and another as acceptor. A crystallographic characterization demonstrates vanadium to iodine charge transfer at ambient temperatures, and the vanadium(III) ground state at low temperature.","In the chromium analogs of the CpMX$\\rm\\sb{n}$ complexes, halogens are unable to oxidize (Cp*CrX$\\sb2\\rbrack\\sb2$ (Cp* = $\\eta\\sp5$-C$\\sb5$Me$\\sb5$) complexes to form mononuclear Cp*CrX$\\sb3$ species. Dioxygen can be activated though to form Cp*CrOX$\\sb2$ compounds. These complexes will catalytically oxidize phosphines (OPR$\\sb3$) and organic sulfides (OSR$\\sb2$) depending upon the type of Cp-group and X. The oxide may be removed by photolysis, thermolysis, or other means resulting in recovery of up to 75% of the starting material.","\"The (Cp*CrX$\\sb2\\rbrack\\sb2$ series may reacted with halogens to form charge transfer complexes such as (Cp*CrX$\\sb2\\rbrack\\sb2\\cdot$X$\\sb2$ (X = Br, I). Both complexes form polymeric solids, but the iodine system displays increased reactivity due to the Lewis acid character of I$\\sb2$. \"\"Cp*CrI$\\sb3$\"\" is a polymer with a distorted polyiodide linkage forming two different (Cp*Cr-I$\\sb2\\rbrack\\sb2$ environments. The iodides are electron rich in this complex, and the polymer will absorb additional iodine. \"\"Cp*CrI$\\sb{5.5}$\"\" has been identified as ((Cp*)$\\sb2$Cr$\\sb2$I$\\sb3\\rbrack\\sb2\\lbrack$I$\\sb{16}\\rbrack,$ an infinite polyiodide network based on the iodine-rich I$\\sb{16}\\sp{2-}$.\"","Made available in DSpace on 2011-05-07T13:20:24Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 8924907.pdf: 6271677 bytes, checksum: ebb952d0206f9ec1b249b2c40a0cd99b (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:53:29Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:24:44-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["High oxidation state organometallics and their charge transfer materials"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Morse, David B."],"dc:date":["2011-05-07T13:20:24Z","10000-01-01","1989"],"dc:description":["This research has been directed toward the systematic design and synthesis of highly oxidizing complexes. These complexes have been used as components in the molecular synthesis of solid state materials displaying cooperative electronic interactions. Complexes of the type CpVX$\\sb3$ (Cp = $\\eta\\sp5$-C$\\rm\\sb5$H$\\sb5$ or -$\\rm C\\sb5H\\sb4$Me; X = Cl, Br) are highly oxidizing. The oxidation potential can be tuned by changes in the cyclopentadienyl ligand, halides, or with a strongly $\\pi$-bonding oxide. Their electronic ground states were characterized.","Reaction of these organometallic acceptors with the organic donor TmTEF (E = S, Se; tetramethyltetrathio(seleno)fulvalene) formed materials such as (TmTTF) ((MeCp)VCl$\\sb3\\rbrack$ and (TmTTF$\\rbrack\\sb3\\lbrack\\{$MeCp) VCl$\\sb2\\}\\sb2$O$\\rbrack\\sb2$. The mixed-valence salt of TmTTF and $\\{$(MeCp)VCl$\\sb2\\}\\sb2$O$\\sp-$ exhibits field dependent magnetic behavior. The single crystal magnetic susceptibility of this one-dimensional solid has defined it as an XY ferromagnet. The low field ferromagnetic response arises from spin alignment within the organometallic fragments. The complex (TmTSF) (CpVBr$\\sb3\\rbrack\\cdot$CH$\\sb2$Cl$\\sb2$ also displays field dependent properties.","Oxidants such as CpVX$\\sb3$ also form partial charge transfer complexes. The organometallic donor Cp$\\sb2$Fe forms a complex with CpVBr$\\sb3$, which exists as Cp$\\sb2$Fe$\\sp+$CpVBr$\\sb3$- in the solid state. CpVI$\\sb3$ forms a charge transfer aggregate in solution wherein one group acts as a donor and another as acceptor. A crystallographic characterization demonstrates vanadium to iodine charge transfer at ambient temperatures, and the vanadium(III) ground state at low temperature.","In the chromium analogs of the CpMX$\\rm\\sb{n}$ complexes, halogens are unable to oxidize (Cp*CrX$\\sb2\\rbrack\\sb2$ (Cp* = $\\eta\\sp5$-C$\\sb5$Me$\\sb5$) complexes to form mononuclear Cp*CrX$\\sb3$ species. Dioxygen can be activated though to form Cp*CrOX$\\sb2$ compounds. These complexes will catalytically oxidize phosphines (OPR$\\sb3$) and organic sulfides (OSR$\\sb2$) depending upon the type of Cp-group and X. The oxide may be removed by photolysis, thermolysis, or other means resulting in recovery of up to 75% of the starting material.","\"The (Cp*CrX$\\sb2\\rbrack\\sb2$ series may reacted with halogens to form charge transfer complexes such as (Cp*CrX$\\sb2\\rbrack\\sb2\\cdot$X$\\sb2$ (X = Br, I). Both complexes form polymeric solids, but the iodine system displays increased reactivity due to the Lewis acid character of I$\\sb2$. \"\"Cp*CrI$\\sb3$\"\" is a polymer with a distorted polyiodide linkage forming two different (Cp*Cr-I$\\sb2\\rbrack\\sb2$ environments. The iodides are electron rich in this complex, and the polymer will absorb additional iodine. \"\"Cp*CrI$\\sb{5.5}$\"\" has been identified as ((Cp*)$\\sb2$Cr$\\sb2$I$\\sb3\\rbrack\\sb2\\lbrack$I$\\sb{16}\\rbrack,$ an infinite polyiodide network based on the iodine-rich I$\\sb{16}\\sp{2-}$.\"","Made available in DSpace on 2011-05-07T13:20:24Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 8924907.pdf: 6271677 bytes, checksum: ebb952d0206f9ec1b249b2c40a0cd99b (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:53:29Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:24:44-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI8924907","(UMI)AAI8924907","http://hdl.handle.net/2142/21829"],"dc:language":["eng"],"dc:rights":["Copyright 1989 Morse, David B."],"dc:subject":["Chemistry, Inorganic"],"dc:title":["High oxidation state organometallics and their charge transfer materials"],"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":"2026-07-22T22:25:18Z"}