{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21604"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21604","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Cyclopentadienyl ruthenium sulfide carbonyls and thiophene activation by iron and rhodium","abstract":"The desulfurization and reduction of the sulfur-containing organic compounds in petroleum products is the objective of catalytic hydrodesulfurization (HDS), one of the largest applications of transition-metal catalysis. However, the specific mechanism for the process is not well understood. This thesis addresses certain aspects of HDS research from an organometallic perspective.","abstract_html":"The desulfurization and reduction of the sulfur-containing organic compounds in petroleum products is the objective of catalytic hydrodesulfurization (HDS), one of the largest applications of transition-metal catalysis. However, the specific mechanism for the process is not well understood. This thesis addresses certain aspects of HDS research from an organometallic perspective.","abstract_has_math":false,"creators":["Ogilvy, Ann Elizabeth"],"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":"2011-05-07T13:13:36Z","date_published":"2011-05-07T13:13:36Z","updated_at":"2026-07-22T22:25:18Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1990 Ogilvy, Ann Elizabeth"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9021737","(UMI)AAI9021737"],"render_values":[{"text":"AAI9021737","href":null,"code":true},{"text":"(UMI)AAI9021737","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21604","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":["Ogilvy, Ann Elizabeth"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:13:36Z","10000-01-01","1990"]},{"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 1990 Ogilvy, Ann Elizabeth"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9021737","(UMI)AAI9021737","http://hdl.handle.net/2142/21604"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The desulfurization and reduction of the sulfur-containing organic compounds in petroleum products is the objective of catalytic hydrodesulfurization (HDS), one of the largest applications of transition-metal catalysis. However, the specific mechanism for the process is not well understood. This thesis addresses certain aspects of HDS research from an organometallic perspective.","A proposed intermediate during thiophene decomposition features thiophene $\\sigma$-bound through an $\\alpha$-carbon to a surface metal atom. Results from the reaction of ($\\rm C\\sb5H\\sb5$)Fe(CO)(PPh$\\sb3$)(2-C$\\sb4$H$\\sb3$S) and methyl triflate indicate the possible formation of two S-methylated configurational isomers. The first non-mercury containing bimetallic $\\mu$-thienyl compound, ((C$\\sb5$H$\\sb5$)Fe(CO)$\\sb2$) $\\sb2$(2,5-C$\\sb4$H$\\sb2$S) was structurally characterized.","The reaction of thiophenic compounds with Fe$\\sb3$(CO)$\\sb{12}$ resulted in metal insertion into the C-S bond. The known benzothiaferrole $\\rm Fe\\sb2(C\\sb8H\\sb6S)(CO)\\sb6$ (1) was hydrogenated to give an insoluble iron-containing solid and a series of ethylbenzene derivatives. Oxidizing agents convert 1 to the carbonylated heterocycle thiocoumarin. $\\rm Fe\\sb2$(2-MeC$\\sb4$H$\\sb3$S)(CO)$\\sb6$ desulfurizes to give the corresponding ferrole complex when heated.","\"$\\rm \\lbrack (C\\sb5 Me\\sb5)Rh(TMT)\\rbrack\\sp{2+}$ (TMT = tetramethylthiophene) reacts with cobaltocene to give the new compound ($\\rm C\\sb5Me\\sb5)Rh(\\eta\\sp4$-TMT), 2. The $\\eta\\sp4$-TMT ligand in 2 desulfurizes upon reaction with Fe$\\sb3$(CO)$\\sb{12}$ to give ($\\rm C\\sb5Me\\sb5)Rh(C\\sb4Me\\sb4)Fe(CO)\\sb3$. An x-ray diffraction study confirms that the Fe(CO)$\\sb3$ fragment is included in the $\\rm C\\sb4Me\\sb4$ ring. The thermolysis of 2 resulted in the formation of an ionic compound. The structurally characterized cation consists of four ($\\rm C\\sb5Me\\sb5)Rh(\\eta\\sp4$-TMT) \"\"units\"\" bound to a central rhodium atom in a square planar fashion creating a \"\"pinwheel\"\" structure. A new mechanism for thiophene HDS was proposed.\"","(($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb6$(CO)$\\sb2$ eliminates SCO to give (($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb5$(CO). (($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb4$ reacts with CO to form (($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb4$(CO) (3). This is the first example of a metal-centered ligand addition to a cyclopentadienyl metal sulfide. The x-ray structure of 3 shows a $\\rm Ru\\sb2S\\sb4$ core in a chair conformation with the bridging ($\\eta\\sp1$-S$\\sb2$) ligands in a trans configuration. In the presence of phosphines, (($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb4$ reacts with CO to form (($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb2$(CO)$\\sb2$.","Made available in DSpace on 2011-05-07T13:13:36Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9021737.pdf: 7105349 bytes, checksum: 21961d6383426492f1f2897f8f320584 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:51:54Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:23:53-05:00 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":["Cyclopentadienyl ruthenium sulfide carbonyls and thiophene activation by iron and rhodium"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Ogilvy, Ann Elizabeth"],"dc:date":["2011-05-07T13:13:36Z","10000-01-01","1990"],"dc:description":["The desulfurization and reduction of the sulfur-containing organic compounds in petroleum products is the objective of catalytic hydrodesulfurization (HDS), one of the largest applications of transition-metal catalysis. However, the specific mechanism for the process is not well understood. This thesis addresses certain aspects of HDS research from an organometallic perspective.","A proposed intermediate during thiophene decomposition features thiophene $\\sigma$-bound through an $\\alpha$-carbon to a surface metal atom. Results from the reaction of ($\\rm C\\sb5H\\sb5$)Fe(CO)(PPh$\\sb3$)(2-C$\\sb4$H$\\sb3$S) and methyl triflate indicate the possible formation of two S-methylated configurational isomers. The first non-mercury containing bimetallic $\\mu$-thienyl compound, ((C$\\sb5$H$\\sb5$)Fe(CO)$\\sb2$) $\\sb2$(2,5-C$\\sb4$H$\\sb2$S) was structurally characterized.","The reaction of thiophenic compounds with Fe$\\sb3$(CO)$\\sb{12}$ resulted in metal insertion into the C-S bond. The known benzothiaferrole $\\rm Fe\\sb2(C\\sb8H\\sb6S)(CO)\\sb6$ (1) was hydrogenated to give an insoluble iron-containing solid and a series of ethylbenzene derivatives. Oxidizing agents convert 1 to the carbonylated heterocycle thiocoumarin. $\\rm Fe\\sb2$(2-MeC$\\sb4$H$\\sb3$S)(CO)$\\sb6$ desulfurizes to give the corresponding ferrole complex when heated.","\"$\\rm \\lbrack (C\\sb5 Me\\sb5)Rh(TMT)\\rbrack\\sp{2+}$ (TMT = tetramethylthiophene) reacts with cobaltocene to give the new compound ($\\rm C\\sb5Me\\sb5)Rh(\\eta\\sp4$-TMT), 2. The $\\eta\\sp4$-TMT ligand in 2 desulfurizes upon reaction with Fe$\\sb3$(CO)$\\sb{12}$ to give ($\\rm C\\sb5Me\\sb5)Rh(C\\sb4Me\\sb4)Fe(CO)\\sb3$. An x-ray diffraction study confirms that the Fe(CO)$\\sb3$ fragment is included in the $\\rm C\\sb4Me\\sb4$ ring. The thermolysis of 2 resulted in the formation of an ionic compound. The structurally characterized cation consists of four ($\\rm C\\sb5Me\\sb5)Rh(\\eta\\sp4$-TMT) \"\"units\"\" bound to a central rhodium atom in a square planar fashion creating a \"\"pinwheel\"\" structure. A new mechanism for thiophene HDS was proposed.\"","(($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb6$(CO)$\\sb2$ eliminates SCO to give (($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb5$(CO). (($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb4$ reacts with CO to form (($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb4$(CO) (3). This is the first example of a metal-centered ligand addition to a cyclopentadienyl metal sulfide. The x-ray structure of 3 shows a $\\rm Ru\\sb2S\\sb4$ core in a chair conformation with the bridging ($\\eta\\sp1$-S$\\sb2$) ligands in a trans configuration. In the presence of phosphines, (($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb4$ reacts with CO to form (($\\rm C\\sb5Me\\sb4Et)Ru$) $\\sb2$S$\\sb2$(CO)$\\sb2$.","Made available in DSpace on 2011-05-07T13:13:36Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9021737.pdf: 7105349 bytes, checksum: 21961d6383426492f1f2897f8f320584 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:51:54Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:23:53-05:00 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":["AAI9021737","(UMI)AAI9021737","http://hdl.handle.net/2142/21604"],"dc:language":["eng"],"dc:rights":["Copyright 1990 Ogilvy, Ann Elizabeth"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Cyclopentadienyl ruthenium sulfide carbonyls and thiophene activation by iron and rhodium"],"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"}