{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/23517"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/23517","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Mobile metal-metal bonds in platinum metal sulfide clusters","abstract":"The thesis presents experimental studies on platinum metal sulfido clusters.","abstract_html":"The thesis presents experimental studies on platinum metal sulfido clusters.","abstract_has_math":false,"creators":["Venturelli, Anne"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry, Inorganic","degree_department":null,"school":null,"contributors":["Rauchfuss, Thomas B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T14:17:08Z","date_published":"2011-05-07T14:17:08Z","updated_at":"2026-07-22T22:25:22Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1996 Venturelli, Anne"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591088908","AAI9702702","(UMI)AAI9702702"],"render_values":[{"text":"9780591088908","href":null,"code":true},{"text":"AAI9702702","href":null,"code":true},{"text":"(UMI)AAI9702702","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/23517","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":["Venturelli, Anne"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T14:17:08Z","10000-01-01","1996"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry, Inorganic"]},{"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 1996 Venturelli, Anne"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591088908","AAI9702702","(UMI)AAI9702702","http://hdl.handle.net/2142/23517"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The thesis presents experimental studies on platinum metal sulfido clusters.","The dicationic complex $\\rm (C\\sb5Me\\sb5)\\sb3Ir\\sb3S\\sb2\\sp{2+}$ was obtained by treatment of $\\rm \\lbrack (\\sb5Me\\sb5)IrCl\\sb2\\rbrack \\sb2$ with $\\rm (Me\\sb3Si)\\sb2S$, followed by purification via aqueous ion exchange chromotography. The dication consists of a trigonal bypyramidal $\\rm Ir\\sb3S\\sb2$ core with Ir-Ir bonds of 2.88 A. Cobaltocene reduction of the salt yielded the neutral clusters. This nido species likely consists of two metal-metal bonds amongst the three edges. Variable temperature $\\sp1$H NMR measurements reveal dynamic behavior of the metal-metal bonds in solution. The $\\sp1$H NMR spectrum consists of two signals in a 2:1 ratio at low temperatures, but only one symmetrical Ir environment at high temperatures. Analogous trinuclear nido clusters of (ring)$\\rm \\sb3M\\sb3S\\sb2$(ring = $\\rm C\\sb5Me\\sb5$, M = Rh; ring = cymene, M = Os) were synthesized and exhibit similar dynamic behavior in solution.","A cuboidal cluster $\\rm (C\\sb5Me\\sb5)\\sb4Ir\\sb4S\\sb4\\sp{2+}$ was also isolated from the reaction of $\\rm \\lbrack(C\\sb5Me\\sb5)IrCl\\sb2\\rbrack \\sb2$ with $\\rm (Me\\sb3Si)\\sb2S$. The tetrairidium dicationic cluster adopts a cubane structure consisting of interpenetrating Ir$\\sb4$ and S$\\sb4$ tetrahedra. The Ir$\\sb4$ core is distorted from an idealized tetrahedrone by one Ir-Ir bond at 2.76 A. Variable temperature $\\sp1$H NMR studies of $\\rm (C\\sb5Me\\sb5)\\sb4Ir\\sb4S\\sb4\\sp{2+}$ indicate that the single metal-metal bond is fluxional in solution. From the dynamic NMR studies, we calculated a $\\Delta$H$\\sp\\ddagger$ value for $\\rm (C\\sb5Me\\sb5)\\sb4Ir\\sb4S\\sb4\\sp{2+}$ of 41 kJ/mol, and $\\Delta$G$\\sp\\ddagger$ of 56 kJ/mol. These values can be compared to those found with $\\rm(C\\sb5Me\\sb5)\\sb4Rh\\sb4S\\sb4\\sp{2+}$ in which $\\Delta$H$\\sp\\ddagger$ is 43 kJ/mol, and $\\Delta$G$\\sp\\ddagger$ is 37 kJ/mol. The $\\Delta$H$\\ddagger$ values for the barrier to single M-M bond migration in the Rh$\\sb4$ and Ir$\\sb4$ clusters are almost the same. DNMR experiments on $\\rm (MeC\\sb5H\\sb4)\\sb4Ru\\sb4S\\sb3(SMe)\\sp+$ also demonstrate the mobility of the metal-metal bonds. The two bonds most likely move in a pairwise fashion. The $\\Delta$H$\\sp\\ddagger$ value for $\\rm (MeC\\sb5H\\sb4)\\sb4Ru\\sb4S\\sb3(SMe)\\sp+$ of 88 kJ/mol suggests that it is more difficult to move a pair of bonds as opposed to a single bond.","Hydrolysis of $\\rm (C\\sb5Me\\sb5)Ir(C\\sb4Me\\sb4S)\\sp{2+}$ with aqueous KOH gives the neutral acylthiolato complex concomitant with cleavage of a C-S bond. Thermolysis of solutions of the iridium acylthiolate led to cleavage of the second C-S bond with the formation of tetramethylfuran and $\\rm (C\\sb5Me\\sb5)\\sb4Ir\\sb4S\\sb4$.","Mixed metal $\\rm M\\sb3S\\sb4$ clusters were obtained by the reaction of $\\rm (C\\sb5R\\sb5)M(CH\\sb3CN)\\sb3\\sp{2+}$ (M = Rh, Ir) with $\\rm (C\\sb5Me\\sb5)\\sb2Ru\\sb2S\\sb4$. The solid state structure of $\\rm \\lbrack (\\sb5Me\\sb5)\\sb3RhRu\\sb2S\\sb4(CH\\sb3CN)\\rbrack \\sp{2+}$ consists of an unsymmetrical $\\rm RhRu\\sb2S\\sb4$ core containing an isosceles triangle of metal atoms with one Ru-Ru bond of 2.88 A. Variable temperature $\\sp1$H NMR spectra reveal that the cluster is fluxional. $\\rm \\lbrack (C\\sb5Me\\sb5)\\sb3RhRu\\sb2S\\sb4(CH\\sb3CN)\\rbrack \\sp{2+}$ reacts with acetone to form the $\\rm \\lbrack (C\\sb5Me\\sb5)\\sb3RhRu\\sb2S\\sb3(SCH\\sb2COCH\\sb3)\\sp+$ species concomitant with cleavage of the C-H bond. This reaction is reversed by the addition of $\\rm HO\\sb3SCF\\sb3$.","Made available in DSpace on 2011-05-07T14:17:08Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702702.pdf: 5124198 bytes, checksum: b5fc7356e6e0750436fd2c7fd728d4e8 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:05:01Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:31:06-05:00 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":["Mobile metal-metal bonds in platinum metal sulfide clusters"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Venturelli, Anne"],"dc:date":["2011-05-07T14:17:08Z","10000-01-01","1996"],"dc:description":["The thesis presents experimental studies on platinum metal sulfido clusters.","The dicationic complex $\\rm (C\\sb5Me\\sb5)\\sb3Ir\\sb3S\\sb2\\sp{2+}$ was obtained by treatment of $\\rm \\lbrack (\\sb5Me\\sb5)IrCl\\sb2\\rbrack \\sb2$ with $\\rm (Me\\sb3Si)\\sb2S$, followed by purification via aqueous ion exchange chromotography. The dication consists of a trigonal bypyramidal $\\rm Ir\\sb3S\\sb2$ core with Ir-Ir bonds of 2.88 A. Cobaltocene reduction of the salt yielded the neutral clusters. This nido species likely consists of two metal-metal bonds amongst the three edges. Variable temperature $\\sp1$H NMR measurements reveal dynamic behavior of the metal-metal bonds in solution. The $\\sp1$H NMR spectrum consists of two signals in a 2:1 ratio at low temperatures, but only one symmetrical Ir environment at high temperatures. Analogous trinuclear nido clusters of (ring)$\\rm \\sb3M\\sb3S\\sb2$(ring = $\\rm C\\sb5Me\\sb5$, M = Rh; ring = cymene, M = Os) were synthesized and exhibit similar dynamic behavior in solution.","A cuboidal cluster $\\rm (C\\sb5Me\\sb5)\\sb4Ir\\sb4S\\sb4\\sp{2+}$ was also isolated from the reaction of $\\rm \\lbrack(C\\sb5Me\\sb5)IrCl\\sb2\\rbrack \\sb2$ with $\\rm (Me\\sb3Si)\\sb2S$. The tetrairidium dicationic cluster adopts a cubane structure consisting of interpenetrating Ir$\\sb4$ and S$\\sb4$ tetrahedra. The Ir$\\sb4$ core is distorted from an idealized tetrahedrone by one Ir-Ir bond at 2.76 A. Variable temperature $\\sp1$H NMR studies of $\\rm (C\\sb5Me\\sb5)\\sb4Ir\\sb4S\\sb4\\sp{2+}$ indicate that the single metal-metal bond is fluxional in solution. From the dynamic NMR studies, we calculated a $\\Delta$H$\\sp\\ddagger$ value for $\\rm (C\\sb5Me\\sb5)\\sb4Ir\\sb4S\\sb4\\sp{2+}$ of 41 kJ/mol, and $\\Delta$G$\\sp\\ddagger$ of 56 kJ/mol. These values can be compared to those found with $\\rm(C\\sb5Me\\sb5)\\sb4Rh\\sb4S\\sb4\\sp{2+}$ in which $\\Delta$H$\\sp\\ddagger$ is 43 kJ/mol, and $\\Delta$G$\\sp\\ddagger$ is 37 kJ/mol. The $\\Delta$H$\\ddagger$ values for the barrier to single M-M bond migration in the Rh$\\sb4$ and Ir$\\sb4$ clusters are almost the same. DNMR experiments on $\\rm (MeC\\sb5H\\sb4)\\sb4Ru\\sb4S\\sb3(SMe)\\sp+$ also demonstrate the mobility of the metal-metal bonds. The two bonds most likely move in a pairwise fashion. The $\\Delta$H$\\sp\\ddagger$ value for $\\rm (MeC\\sb5H\\sb4)\\sb4Ru\\sb4S\\sb3(SMe)\\sp+$ of 88 kJ/mol suggests that it is more difficult to move a pair of bonds as opposed to a single bond.","Hydrolysis of $\\rm (C\\sb5Me\\sb5)Ir(C\\sb4Me\\sb4S)\\sp{2+}$ with aqueous KOH gives the neutral acylthiolato complex concomitant with cleavage of a C-S bond. Thermolysis of solutions of the iridium acylthiolate led to cleavage of the second C-S bond with the formation of tetramethylfuran and $\\rm (C\\sb5Me\\sb5)\\sb4Ir\\sb4S\\sb4$.","Mixed metal $\\rm M\\sb3S\\sb4$ clusters were obtained by the reaction of $\\rm (C\\sb5R\\sb5)M(CH\\sb3CN)\\sb3\\sp{2+}$ (M = Rh, Ir) with $\\rm (C\\sb5Me\\sb5)\\sb2Ru\\sb2S\\sb4$. The solid state structure of $\\rm \\lbrack (\\sb5Me\\sb5)\\sb3RhRu\\sb2S\\sb4(CH\\sb3CN)\\rbrack \\sp{2+}$ consists of an unsymmetrical $\\rm RhRu\\sb2S\\sb4$ core containing an isosceles triangle of metal atoms with one Ru-Ru bond of 2.88 A. Variable temperature $\\sp1$H NMR spectra reveal that the cluster is fluxional. $\\rm \\lbrack (C\\sb5Me\\sb5)\\sb3RhRu\\sb2S\\sb4(CH\\sb3CN)\\rbrack \\sp{2+}$ reacts with acetone to form the $\\rm \\lbrack (C\\sb5Me\\sb5)\\sb3RhRu\\sb2S\\sb3(SCH\\sb2COCH\\sb3)\\sp+$ species concomitant with cleavage of the C-H bond. This reaction is reversed by the addition of $\\rm HO\\sb3SCF\\sb3$.","Made available in DSpace on 2011-05-07T14:17:08Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702702.pdf: 5124198 bytes, checksum: b5fc7356e6e0750436fd2c7fd728d4e8 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:05:01Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:31:06-05:00 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":["9780591088908","AAI9702702","(UMI)AAI9702702","http://hdl.handle.net/2142/23517"],"dc:language":["eng"],"dc:rights":["Copyright 1996 Venturelli, Anne"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Mobile metal-metal bonds in platinum metal sulfide clusters"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry, Inorganic"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:22Z"}