{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/23155"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/23155","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Cysteine(2-), alkyl, and siloxide complexes of ruthenium(VI) and iron(III)","abstract":"Transition metal-cysteine complexes are reviewed in Chapter 1. Compounds for which X-ray crystal structures have been determined are considered first followed by those for which only spectroscopic evidence exists. The synthesis and characterization of several trans-dioxoruthenium(VI) species containing cysteine(2$-)$ and related ligands is reported in Chapter 2. The compounds $\\rm Ru(O)\\sb2(py)\\sb2(SC\\sb2H\\sb5)\\sb2,$ Ru(O)$\\sb2$(py)$\\sb2\\{$SCH$\\sb2$CH$\\sb2$C(O)O$\\},$ Ru(O)$\\sb2$(bpy)$\\{$SCH$\\sb2$CH(NCHO)C(O)O$\\},$ Ru(O)$\\sb2$(py)$\\{$SCH$\\sb2$CH(NHCOMe)C(O)O$\\},$ and Ru(O)$\\sb2$(bpy)$\\{$SCH$\\sb2$CH(NHCOMe)C(O)O$\\}$ have been synthesized in yields ranging from 60-87% from Ru(O)$\\sb2$(OH)$\\sb2$(py)$\\sb2$ and Ru(O)$\\sb2$Cl$\\sb2$(bpy) using either ethane thiol, 3-mercaptopropionic acid, N-acetyl-L-cysteine, or N-formyl-L-cysteine. The iron(II) and iron(III) complexes (NBu$\\sb4\\rbrack\\sb{\\rm n}$ (Fe(SCH$\\sb2$CH(NHCOCH$\\sb3)$COO)$\\sb2$) (n = 1,2) have been synthesized by the addition of two equivalents of N-aceteyl-L-cysteine to methylene chloride solutions of either (NBu$\\sb4$) (Fe$\\sp{\\rm III}$(OSiMe$\\sb3)\\sb4$) or (NBu$\\sb4\\rbrack\\sb2$(Fe$\\sp{\\rm II}$(OSiMe$\\sb3)\\sb4$) and are described in Chapter 3. The synthesis and characterization of the first monooxo ruthenium(VI) tetraalkyl complex, (Ru(O)(CH$\\sb2$Si(CH$\\sb3)\\sb3)\\sb4$), is reported in Chapter 4 along with that for Ru(CH$\\sb2$Si(CH$\\sb3)\\sb3)\\sb4.$ These complexes are readily synthesized from trans-(PPN) $\\sb2$(Ru(O)$\\sb2$Cl$\\sb4$) and either four or ten equivalents of trimethylsilyl-methylmagnesium chloride in THF or methylene chloride respectively. In Chapter 5, combination of (C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$H$\\sb3$ with either (NBu$\\sb4$) (Fe(OSiMe$\\sb3)\\sb4$) or (NBu$\\sb4$) (Fe(Cl)$\\sb4$) and triethylamine gives the iron-containing silsesquioxanes (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeCl) and (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeOSi(CH$\\sb3)\\sb3$) in yields of at least 60% after recrystallization from toluene/hexane. These complexes can be modified by substitution for the free siloxide or chloride ligand to give (NBu$\\sb4$) ($\\{$(C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$Fe$\\}\\sb2$O), (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeOOC(CH$\\sb3)\\sb3$), and (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$Fe(S-cysteine-OMe)).","abstract_html":"Transition metal-cysteine complexes are reviewed in Chapter 1. Compounds for which X-ray crystal structures have been determined are considered first followed by those for which only spectroscopic evidence exists. The synthesis and characterization of several trans-dioxoruthenium(VI) species containing cysteine(2$-)$ and related ligands is reported in Chapter 2. The compounds $\\rm Ru(O)\\sb2(py)\\sb2(SC\\sb2H\\sb5)\\sb2,$ Ru(O)$\\sb2$(py)$\\sb2\\{$SCH$\\sb2$CH$\\sb2$C(O)O$\\},$ Ru(O)$\\sb2$(bpy)$\\{$SCH$\\sb2$CH(NCHO)C(O)O$\\},$ Ru(O)$\\sb2$(py)$\\{$SCH$\\sb2$CH(NHCOMe)C(O)O$\\},$ and Ru(O)$\\sb2$(bpy)$\\{$SCH$\\sb2$CH(NHCOMe)C(O)O$\\}$ have been synthesized in yields ranging from 60-87% from Ru(O)$\\sb2$(OH)$\\sb2$(py)$\\sb2$ and Ru(O)$\\sb2$Cl$\\sb2$(bpy) using either ethane thiol, 3-mercaptopropionic acid, N-acetyl-L-cysteine, or N-formyl-L-cysteine. The iron(II) and iron(III) complexes (NBu$\\sb4\\rbrack\\sb{\\rm n}$ (Fe(SCH$\\sb2$CH(NHCOCH$\\sb3)$COO)$\\sb2$) (n = 1,2) have been synthesized by the addition of two equivalents of N-aceteyl-L-cysteine to methylene chloride solutions of either (NBu$\\sb4$) (Fe$\\sp{\\rm III}$(OSiMe$\\sb3)\\sb4$) or (NBu$\\sb4\\rbrack\\sb2$(Fe$\\sp{\\rm II}$(OSiMe$\\sb3)\\sb4$) and are described in Chapter 3. The synthesis and characterization of the first monooxo ruthenium(VI) tetraalkyl complex, (Ru(O)(CH$\\sb2$Si(CH$\\sb3)\\sb3)\\sb4$), is reported in Chapter 4 along with that for Ru(CH$\\sb2$Si(CH$\\sb3)\\sb3)\\sb4.$ These complexes are readily synthesized from trans-(PPN) $\\sb2$(Ru(O)$\\sb2$Cl$\\sb4$) and either four or ten equivalents of trimethylsilyl-methylmagnesium chloride in THF or methylene chloride respectively. In Chapter 5, combination of (C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$H$\\sb3$ with either (NBu$\\sb4$) (Fe(OSiMe$\\sb3)\\sb4$) or (NBu$\\sb4$) (Fe(Cl)$\\sb4$) and triethylamine gives the iron-containing silsesquioxanes (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeCl) and (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeOSi(CH$\\sb3)\\sb3$) in yields of at least 60% after recrystallization from toluene/hexane. These complexes can be modified by substitution for the free siloxide or chloride ligand to give (NBu$\\sb4$) ($\\{$(C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$Fe$\\}\\sb2$O), (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeOOC(CH$\\sb3)\\sb3$), and (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$Fe(S-cysteine-OMe)).","abstract_has_math":true,"creators":["Bigham, Wilson Stuart"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Shapley, Patricia A."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T14:04:07Z","date_published":"2011-05-07T14:04:07Z","updated_at":"2026-07-22T22:25:21Z","subjects":["Chemistry, Inorganic","Chemistry, Organic"],"languages":["eng"],"rights":["Copyright 1992 Bigham, Wilson Stuart"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9236397","(UMI)AAI9236397"],"render_values":[{"text":"AAI9236397","href":null,"code":true},{"text":"(UMI)AAI9236397","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/23155","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Shapley, Patricia A."]},{"key":"dc:creator","label":"Author","values":["Bigham, Wilson Stuart"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T14:04:07Z","10000-01-01","1992"]},{"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","Chemistry, Organic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1992 Bigham, Wilson Stuart"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9236397","(UMI)AAI9236397","http://hdl.handle.net/2142/23155"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Transition metal-cysteine complexes are reviewed in Chapter 1. Compounds for which X-ray crystal structures have been determined are considered first followed by those for which only spectroscopic evidence exists. The synthesis and characterization of several trans-dioxoruthenium(VI) species containing cysteine(2$-)$ and related ligands is reported in Chapter 2. The compounds $\\rm Ru(O)\\sb2(py)\\sb2(SC\\sb2H\\sb5)\\sb2,$ Ru(O)$\\sb2$(py)$\\sb2\\{$SCH$\\sb2$CH$\\sb2$C(O)O$\\},$ Ru(O)$\\sb2$(bpy)$\\{$SCH$\\sb2$CH(NCHO)C(O)O$\\},$ Ru(O)$\\sb2$(py)$\\{$SCH$\\sb2$CH(NHCOMe)C(O)O$\\},$ and Ru(O)$\\sb2$(bpy)$\\{$SCH$\\sb2$CH(NHCOMe)C(O)O$\\}$ have been synthesized in yields ranging from 60-87% from Ru(O)$\\sb2$(OH)$\\sb2$(py)$\\sb2$ and Ru(O)$\\sb2$Cl$\\sb2$(bpy) using either ethane thiol, 3-mercaptopropionic acid, N-acetyl-L-cysteine, or N-formyl-L-cysteine. The iron(II) and iron(III) complexes (NBu$\\sb4\\rbrack\\sb{\\rm n}$ (Fe(SCH$\\sb2$CH(NHCOCH$\\sb3)$COO)$\\sb2$) (n = 1,2) have been synthesized by the addition of two equivalents of N-aceteyl-L-cysteine to methylene chloride solutions of either (NBu$\\sb4$) (Fe$\\sp{\\rm III}$(OSiMe$\\sb3)\\sb4$) or (NBu$\\sb4\\rbrack\\sb2$(Fe$\\sp{\\rm II}$(OSiMe$\\sb3)\\sb4$) and are described in Chapter 3. The synthesis and characterization of the first monooxo ruthenium(VI) tetraalkyl complex, (Ru(O)(CH$\\sb2$Si(CH$\\sb3)\\sb3)\\sb4$), is reported in Chapter 4 along with that for Ru(CH$\\sb2$Si(CH$\\sb3)\\sb3)\\sb4.$ These complexes are readily synthesized from trans-(PPN) $\\sb2$(Ru(O)$\\sb2$Cl$\\sb4$) and either four or ten equivalents of trimethylsilyl-methylmagnesium chloride in THF or methylene chloride respectively. In Chapter 5, combination of (C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$H$\\sb3$ with either (NBu$\\sb4$) (Fe(OSiMe$\\sb3)\\sb4$) or (NBu$\\sb4$) (Fe(Cl)$\\sb4$) and triethylamine gives the iron-containing silsesquioxanes (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeCl) and (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeOSi(CH$\\sb3)\\sb3$) in yields of at least 60% after recrystallization from toluene/hexane. These complexes can be modified by substitution for the free siloxide or chloride ligand to give (NBu$\\sb4$) ($\\{$(C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$Fe$\\}\\sb2$O), (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeOOC(CH$\\sb3)\\sb3$), and (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$Fe(S-cysteine-OMe)).","Made available in DSpace on 2011-05-07T14:04:07Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9236397.pdf: 5133594 bytes, checksum: a6f03ffd2a0fb143fbba73c6830b62c8 (MD5) Previous issue date: 1992","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:02:33Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:29:45-05:00 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":["Cysteine(2-), alkyl, and siloxide complexes of ruthenium(VI) and iron(III)"]}]}],"canonical_facts":{"dc:contributor":["Shapley, Patricia A."],"dc:creator":["Bigham, Wilson Stuart"],"dc:date":["2011-05-07T14:04:07Z","10000-01-01","1992"],"dc:description":["Transition metal-cysteine complexes are reviewed in Chapter 1. Compounds for which X-ray crystal structures have been determined are considered first followed by those for which only spectroscopic evidence exists. The synthesis and characterization of several trans-dioxoruthenium(VI) species containing cysteine(2$-)$ and related ligands is reported in Chapter 2. The compounds $\\rm Ru(O)\\sb2(py)\\sb2(SC\\sb2H\\sb5)\\sb2,$ Ru(O)$\\sb2$(py)$\\sb2\\{$SCH$\\sb2$CH$\\sb2$C(O)O$\\},$ Ru(O)$\\sb2$(bpy)$\\{$SCH$\\sb2$CH(NCHO)C(O)O$\\},$ Ru(O)$\\sb2$(py)$\\{$SCH$\\sb2$CH(NHCOMe)C(O)O$\\},$ and Ru(O)$\\sb2$(bpy)$\\{$SCH$\\sb2$CH(NHCOMe)C(O)O$\\}$ have been synthesized in yields ranging from 60-87% from Ru(O)$\\sb2$(OH)$\\sb2$(py)$\\sb2$ and Ru(O)$\\sb2$Cl$\\sb2$(bpy) using either ethane thiol, 3-mercaptopropionic acid, N-acetyl-L-cysteine, or N-formyl-L-cysteine. The iron(II) and iron(III) complexes (NBu$\\sb4\\rbrack\\sb{\\rm n}$ (Fe(SCH$\\sb2$CH(NHCOCH$\\sb3)$COO)$\\sb2$) (n = 1,2) have been synthesized by the addition of two equivalents of N-aceteyl-L-cysteine to methylene chloride solutions of either (NBu$\\sb4$) (Fe$\\sp{\\rm III}$(OSiMe$\\sb3)\\sb4$) or (NBu$\\sb4\\rbrack\\sb2$(Fe$\\sp{\\rm II}$(OSiMe$\\sb3)\\sb4$) and are described in Chapter 3. The synthesis and characterization of the first monooxo ruthenium(VI) tetraalkyl complex, (Ru(O)(CH$\\sb2$Si(CH$\\sb3)\\sb3)\\sb4$), is reported in Chapter 4 along with that for Ru(CH$\\sb2$Si(CH$\\sb3)\\sb3)\\sb4.$ These complexes are readily synthesized from trans-(PPN) $\\sb2$(Ru(O)$\\sb2$Cl$\\sb4$) and either four or ten equivalents of trimethylsilyl-methylmagnesium chloride in THF or methylene chloride respectively. In Chapter 5, combination of (C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$H$\\sb3$ with either (NBu$\\sb4$) (Fe(OSiMe$\\sb3)\\sb4$) or (NBu$\\sb4$) (Fe(Cl)$\\sb4$) and triethylamine gives the iron-containing silsesquioxanes (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeCl) and (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeOSi(CH$\\sb3)\\sb3$) in yields of at least 60% after recrystallization from toluene/hexane. These complexes can be modified by substitution for the free siloxide or chloride ligand to give (NBu$\\sb4$) ($\\{$(C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$Fe$\\}\\sb2$O), (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$FeOOC(CH$\\sb3)\\sb3$), and (NBu$\\sb4$) ((C$\\sb5$H$\\sb9)\\sb7$Si$\\sb7$O$\\sb{12}$Fe(S-cysteine-OMe)).","Made available in DSpace on 2011-05-07T14:04:07Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9236397.pdf: 5133594 bytes, checksum: a6f03ffd2a0fb143fbba73c6830b62c8 (MD5) Previous issue date: 1992","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:02:33Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:29:45-05:00 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":["AAI9236397","(UMI)AAI9236397","http://hdl.handle.net/2142/23155"],"dc:language":["eng"],"dc:rights":["Copyright 1992 Bigham, Wilson Stuart"],"dc:subject":["Chemistry, Inorganic","Chemistry, Organic"],"dc:title":["Cysteine(2-), alkyl, and siloxide complexes of ruthenium(VI) and iron(III)"],"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":"2026-07-22T22:25:21Z"}