{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21437"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21437","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The synthesis and stereodynamics of cyclopentadienyl ruthenium chalcogenide clusters","abstract":"A diamagnetic salt of the (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4\\sp{2+}$ cluster cation was obtained by oxidation of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4$ with ((MeC$\\sb5$H$\\sb4)\\sb2$Fe) PF$\\sb6$. Variable temperature $\\sp1$H NMR measurements showed that (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4\\sp{2+}$ is dynamic in solution; it exhibits signals for two chiral Ru sites at low temperatures but only one symmetrical Ru environment at high temperatures. Similar dynamic behavior was observed for (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$Se$\\sb4$(PF$\\sb6)\\sb2$, while samples of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$Te$\\sb4$(PF$\\sb6)\\sb2$ showed only slight line broadening at low temperatures. The concentration independence of the coalescence temperature (T$\\sb{\\rm c}$) of the CH$\\sb3$C$\\sb5$H$\\sb4$ signals showed that the exchange processes are intramolecular. The exchange barrier of (Me$\\sb3$SiC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4$(PF$\\sb6)\\sb2$ was found to be similar to those of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$E$\\sb4$(PF$\\sb6)\\sb2$ (E = S, Se), which indicates that the exchange processes do not involve hindered RCp rotation. The activation parameters were evaluated from analyses of the line shapes as a function of temperature; the free energies of activation range from 52 to 55 kJ/mol for all clusters.","abstract_html":"A diamagnetic salt of the (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4\\sp{2+}$ cluster cation was obtained by oxidation of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4$ with ((MeC$\\sb5$H$\\sb4)\\sb2$Fe) PF$\\sb6$. Variable temperature $\\sp1$H NMR measurements showed that (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4\\sp{2+}$ is dynamic in solution; it exhibits signals for two chiral Ru sites at low temperatures but only one symmetrical Ru environment at high temperatures. Similar dynamic behavior was observed for (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$Se$\\sb4$(PF$\\sb6)\\sb2$, while samples of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$Te$\\sb4$(PF$\\sb6)\\sb2$ showed only slight line broadening at low temperatures. The concentration independence of the coalescence temperature (T$\\sb{\\rm c}$) of the CH$\\sb3$C$\\sb5$H$\\sb4$ signals showed that the exchange processes are intramolecular. The exchange barrier of (Me$\\sb3$SiC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4$(PF$\\sb6)\\sb2$ was found to be similar to those of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$E$\\sb4$(PF$\\sb6)\\sb2$ (E = S, Se), which indicates that the exchange processes do not involve hindered RCp rotation. The activation parameters were evaluated from analyses of the line shapes as a function of temperature; the free energies of activation range from 52 to 55 kJ/mol for all clusters.","abstract_has_math":true,"creators":["Houser, Eric Jon"],"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":"2011-05-07T13:08:37Z","date_published":"2011-05-07T13:08:37Z","updated_at":"2026-07-22T22:25:18Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1994 Houser, Eric Jon"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9416373","(UMI)AAI9416373"],"render_values":[{"text":"AAI9416373","href":null,"code":true},{"text":"(UMI)AAI9416373","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21437","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":["Houser, Eric Jon"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:08:37Z","10000-01-01","1994"]},{"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 1994 Houser, Eric Jon"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9416373","(UMI)AAI9416373","http://hdl.handle.net/2142/21437"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["A diamagnetic salt of the (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4\\sp{2+}$ cluster cation was obtained by oxidation of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4$ with ((MeC$\\sb5$H$\\sb4)\\sb2$Fe) PF$\\sb6$. Variable temperature $\\sp1$H NMR measurements showed that (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4\\sp{2+}$ is dynamic in solution; it exhibits signals for two chiral Ru sites at low temperatures but only one symmetrical Ru environment at high temperatures. Similar dynamic behavior was observed for (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$Se$\\sb4$(PF$\\sb6)\\sb2$, while samples of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$Te$\\sb4$(PF$\\sb6)\\sb2$ showed only slight line broadening at low temperatures. The concentration independence of the coalescence temperature (T$\\sb{\\rm c}$) of the CH$\\sb3$C$\\sb5$H$\\sb4$ signals showed that the exchange processes are intramolecular. The exchange barrier of (Me$\\sb3$SiC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4$(PF$\\sb6)\\sb2$ was found to be similar to those of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$E$\\sb4$(PF$\\sb6)\\sb2$ (E = S, Se), which indicates that the exchange processes do not involve hindered RCp rotation. The activation parameters were evaluated from analyses of the line shapes as a function of temperature; the free energies of activation range from 52 to 55 kJ/mol for all clusters.","((MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb3$(SCH$\\sb3)$) CF$\\sb3$SO$\\sb3$ was obtained by the reaction of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4$ with CH$\\sb3$SO$\\sb3$CF$\\sb3$. Oxidation of ((MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb3$(SCH$\\sb3$)) CF$\\sb3$SO$\\sb3$ with (Cp$\\sb2$Fe) PF$\\sb6$ yielded ((MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb3$(SCH$\\sb3$)) (PF$\\sb6)\\sb2$CF$\\sb3$SO$\\sb3$. Both clusters exhibited dynamic behavior.","Salts of (C$\\sb5$Me$\\sb5)\\sb3$Ru$\\sb3$S$\\sb4\\sp+$ were obtained by reaction of (C$\\sb5$Me$\\sb5$)Ru(CH$\\sb3$CN)$\\sb3\\sp+$ with (C$\\sb5$Me$\\sb5)\\sb2$Ru$\\sb2$S$\\sb4$. The solid state structure of (C$\\sb5$Me$\\sb5)\\sb3$Ru$\\sb3$S$\\sb4$(PF$\\sb6$) showed that the cluster cation contains a new bonding mode for a persulfide ligand and defines a new structural motif for M$\\sb3$S$\\sb4$ clusters. Electrophiles react with (C$\\sb5$Me$\\sb5)\\sb3$Ru$\\sb3$S$\\sb4\\sp+$ and add to the bridging sulfur atoms. The core structure of the SO$\\sb2$ adduct (C$\\sb5$Me$\\sb5)\\sb3$Ru$\\sb3$S$\\sb3$(S$\\sb2$O$\\sb2)\\sp+$ differs from that of (C$\\sb5$Me$\\sb5)\\sb3$Ru$\\sb3$S$\\sb4\\sp+$ in that it only has one persulfide ligand.","The reaction of tetramethyltetrathiafulvalene (TMTTF) with Fe$\\sb4$S$\\sb4$(NO)$\\sb4$ gave the one-dimensional charge transfer salt (TMTTF)$\\sb2$Fe$\\sb4$S$\\sb4$(NO)$\\sb4$. Solid state measurements showed this material to be a paramagnetic semiconductor.","Made available in DSpace on 2011-05-07T13:08:37Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9416373.pdf: 7355376 bytes, checksum: fffdd35eb76b8271cea13874eb32fe90 (MD5) Previous issue date: 1994","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:50:46Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:23:14-05:00 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":["The synthesis and stereodynamics of cyclopentadienyl ruthenium chalcogenide clusters"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Houser, Eric Jon"],"dc:date":["2011-05-07T13:08:37Z","10000-01-01","1994"],"dc:description":["A diamagnetic salt of the (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4\\sp{2+}$ cluster cation was obtained by oxidation of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4$ with ((MeC$\\sb5$H$\\sb4)\\sb2$Fe) PF$\\sb6$. Variable temperature $\\sp1$H NMR measurements showed that (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4\\sp{2+}$ is dynamic in solution; it exhibits signals for two chiral Ru sites at low temperatures but only one symmetrical Ru environment at high temperatures. Similar dynamic behavior was observed for (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$Se$\\sb4$(PF$\\sb6)\\sb2$, while samples of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$Te$\\sb4$(PF$\\sb6)\\sb2$ showed only slight line broadening at low temperatures. The concentration independence of the coalescence temperature (T$\\sb{\\rm c}$) of the CH$\\sb3$C$\\sb5$H$\\sb4$ signals showed that the exchange processes are intramolecular. The exchange barrier of (Me$\\sb3$SiC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4$(PF$\\sb6)\\sb2$ was found to be similar to those of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$E$\\sb4$(PF$\\sb6)\\sb2$ (E = S, Se), which indicates that the exchange processes do not involve hindered RCp rotation. The activation parameters were evaluated from analyses of the line shapes as a function of temperature; the free energies of activation range from 52 to 55 kJ/mol for all clusters.","((MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb3$(SCH$\\sb3)$) CF$\\sb3$SO$\\sb3$ was obtained by the reaction of (MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb4$ with CH$\\sb3$SO$\\sb3$CF$\\sb3$. Oxidation of ((MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb3$(SCH$\\sb3$)) CF$\\sb3$SO$\\sb3$ with (Cp$\\sb2$Fe) PF$\\sb6$ yielded ((MeC$\\sb5$H$\\sb4)\\sb4$Ru$\\sb4$S$\\sb3$(SCH$\\sb3$)) (PF$\\sb6)\\sb2$CF$\\sb3$SO$\\sb3$. Both clusters exhibited dynamic behavior.","Salts of (C$\\sb5$Me$\\sb5)\\sb3$Ru$\\sb3$S$\\sb4\\sp+$ were obtained by reaction of (C$\\sb5$Me$\\sb5$)Ru(CH$\\sb3$CN)$\\sb3\\sp+$ with (C$\\sb5$Me$\\sb5)\\sb2$Ru$\\sb2$S$\\sb4$. The solid state structure of (C$\\sb5$Me$\\sb5)\\sb3$Ru$\\sb3$S$\\sb4$(PF$\\sb6$) showed that the cluster cation contains a new bonding mode for a persulfide ligand and defines a new structural motif for M$\\sb3$S$\\sb4$ clusters. Electrophiles react with (C$\\sb5$Me$\\sb5)\\sb3$Ru$\\sb3$S$\\sb4\\sp+$ and add to the bridging sulfur atoms. The core structure of the SO$\\sb2$ adduct (C$\\sb5$Me$\\sb5)\\sb3$Ru$\\sb3$S$\\sb3$(S$\\sb2$O$\\sb2)\\sp+$ differs from that of (C$\\sb5$Me$\\sb5)\\sb3$Ru$\\sb3$S$\\sb4\\sp+$ in that it only has one persulfide ligand.","The reaction of tetramethyltetrathiafulvalene (TMTTF) with Fe$\\sb4$S$\\sb4$(NO)$\\sb4$ gave the one-dimensional charge transfer salt (TMTTF)$\\sb2$Fe$\\sb4$S$\\sb4$(NO)$\\sb4$. Solid state measurements showed this material to be a paramagnetic semiconductor.","Made available in DSpace on 2011-05-07T13:08:37Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9416373.pdf: 7355376 bytes, checksum: fffdd35eb76b8271cea13874eb32fe90 (MD5) Previous issue date: 1994","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:50:46Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:23:14-05:00 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":["AAI9416373","(UMI)AAI9416373","http://hdl.handle.net/2142/21437"],"dc:language":["eng"],"dc:rights":["Copyright 1994 Houser, Eric Jon"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["The synthesis and stereodynamics of cyclopentadienyl ruthenium chalcogenide clusters"],"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"}