{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/72283"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/72283","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Chemistry of Ruthenium and Rhodium Eta(4)-Thiophene Complexes","abstract":"Reduction of ($(\\eta\\sp6$-$\\rm C\\sb6Me\\sb6)Ru(\\eta\\sp5$-C$\\sb4$R$\\sb4$S)) (OTf)$\\sb2$(C$\\sb4$R$\\sb4$S = C$\\sb4$H$\\sb4$S (1a), 2,5-Me$\\sb2$C$\\sb4$H$\\sb2$S (1b), and 2,3,4,5-Me$\\sb4$C$\\sb4$S (1c)) and (($\\eta\\sp5$-C$\\sb4$Me$\\sb4$S)$\\sb2$Ru) (OTf)$\\sb2$ (1d) with Cp$\\sb2$Co produces (arene)Ru($\\eta\\sp4$-C$\\sb4$R$\\sb4$S) (2a-d). 2d is unstable $>-20\\sp\\circ$C. It reacts with Fe(CO)$\\sb5$ in the presence of Me$\\sb3$NO to yield the thermally stable $(\\eta\\sp5$-$\\rm C\\sb4Me\\sb4S)Ru(\\eta\\sp4{:}\\eta\\sp1$-$\\rm C\\sb4Me\\sb4S)Fe(CO)\\sb4$(2d$\\cdot$Fe(CO)$\\sb4).$","abstract_html":"Reduction of ($(\\eta\\sp6$-$\\rm C\\sb6Me\\sb6)Ru(\\eta\\sp5$-C$\\sb4$R$\\sb4$S)) (OTf)$\\sb2$(C$\\sb4$R$\\sb4$S = C$\\sb4$H$\\sb4$S (1a), 2,5-Me$\\sb2$C$\\sb4$H$\\sb2$S (1b), and 2,3,4,5-Me$\\sb4$C$\\sb4$S (1c)) and (($\\eta\\sp5$-C$\\sb4$Me$\\sb4$S)$\\sb2$Ru) (OTf)$\\sb2$ (1d) with Cp$\\sb2$Co produces (arene)Ru($\\eta\\sp4$-C$\\sb4$R$\\sb4$S) (2a-d). 2d is unstable $>-20\\sp\\circ$C. It reacts with Fe(CO)$\\sb5$ in the presence of Me$\\sb3$NO to yield the thermally stable $(\\eta\\sp5$-$\\rm C\\sb4Me\\sb4S)Ru(\\eta\\sp4{:}\\eta\\sp1$-$\\rm C\\sb4Me\\sb4S)Fe(CO)\\sb4$(2d$\\cdot$Fe(CO)$\\sb4).$","abstract_has_math":true,"creators":["Luo, Shifang"],"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":2014,"date_issued":"2014-12-17T21:29:07Z","date_published":"2014-12-17T21:29:07Z","updated_at":"2026-07-22T22:26:06Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI9329104"],"render_values":[{"text":"(UMI)AAI9329104","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/72283","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":["Luo, Shifang"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-17T21:29:07Z","10000-01-01","1993"]},{"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":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/72283","(UMI)AAI9329104"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Reduction of ($(\\eta\\sp6$-$\\rm C\\sb6Me\\sb6)Ru(\\eta\\sp5$-C$\\sb4$R$\\sb4$S)) (OTf)$\\sb2$(C$\\sb4$R$\\sb4$S = C$\\sb4$H$\\sb4$S (1a), 2,5-Me$\\sb2$C$\\sb4$H$\\sb2$S (1b), and 2,3,4,5-Me$\\sb4$C$\\sb4$S (1c)) and (($\\eta\\sp5$-C$\\sb4$Me$\\sb4$S)$\\sb2$Ru) (OTf)$\\sb2$ (1d) with Cp$\\sb2$Co produces (arene)Ru($\\eta\\sp4$-C$\\sb4$R$\\sb4$S) (2a-d). 2d is unstable $>-20\\sp\\circ$C. It reacts with Fe(CO)$\\sb5$ in the presence of Me$\\sb3$NO to yield the thermally stable $(\\eta\\sp5$-$\\rm C\\sb4Me\\sb4S)Ru(\\eta\\sp4{:}\\eta\\sp1$-$\\rm C\\sb4Me\\sb4S)Fe(CO)\\sb4$(2d$\\cdot$Fe(CO)$\\sb4).$","Thermolysis of (C$\\sb5$Me$\\sb5$)Rh($\\eta\\sp4$-C$\\sb4$Me$\\sb4$S) (2e) gives $(\\rm C\\sb5Me\\sb5)\\sb3Rh\\sb3 (\\eta\\sp4{:}\\eta\\sp1$-C$\\sb4$Me$\\sb4$S)$\\sb2$ (3) and C$\\sb4$Me$\\sb4$S. 3 further decomposes to give (C$\\sb5$Me$\\sb5)\\sb2$Rh$\\sb2$(C$\\sb4$Me$\\sb4$S) (4). Thermolysis of 2c in non-aromatic solvents such as hexane produces (C$\\sb6$Me$\\sb6)\\sb3$Ru$\\sb3$ $(\\eta\\sp4{:}\\eta\\sp1$-C$\\sb4$Me$\\sb4$S)$\\sb2$ (5a). In aromatic solvents, thermolysis of 2c yields the arene exchange products $(\\eta\\sp6$-solvent)(C$\\sb6$Me$\\sb6) \\sb2$Ru$\\sb3(\\eta\\sp4{:}\\eta\\sp1$-C$\\sb4$Me$\\sb4$S)$\\sb2$ (solvent = C$\\sb6$D$\\sb6$ (5b), toluene (5c)) at low concentrations while at high concentrations it yields both 5a and 5b (in C$\\sb6$D$\\sb6$) or 5c (in toluene). In the presence of H$\\sb2$, 2c decomposes to give (C$\\sb6$Me$\\sb6)\\sb2$Ru$\\sb2$ $(\\eta\\sp4{:}\\eta\\sp1$-C$\\sb4$Me$\\sb4$S)(H)$\\sb2$ (6).","Protonation of 2a-c with NH$\\sb4$PF$\\sb6$ affords (($\\eta\\sp6$-$\\rm C\\sb6Me\\sb6)Ru(\\eta\\sp4$-2-H-C$\\sb4$R$\\sb4$S)) PF$\\sb6$ (7a-c). The added proton is in the endo position of the carbon $\\alpha$ to sulfur. Protonation of 2d with NH$\\sb4$PF$\\sb6$ also affords the analogous ($(\\eta\\sp5$-C$\\sb5$Me$\\sb5$)Rh($\\eta\\sp4$-$2$ -H-C$\\sb4$Me$\\sb4$S)) PF$\\sb6$ (7d). Complex 7a undergoes C-S bond cleavage both in solution and the solid state to afford the thiapentadienyl complex (($\\eta\\sp6$-$\\rm C\\sb6Me\\sb6)Ru(\\eta\\sp5$-CH$\\sb2$=CH-CH=CH-S)) PF$\\sb6$ (8).","Complex 2e reacts with Fe$\\sb3$(CO)$\\sb $ to give (C$\\sb5$Me$\\sb5$)Rh$\\{\\eta\\sp5$-C$\\sb4$Me$\\sb4$Fe(CO)$\\sb3\\}$ (9) and (C$\\sb5$Me$\\sb5$)Rh($\\eta\\sp4$:$\\eta\\sp1$-C$\\sb4$Me$\\sb4$S)Fe(CO)$\\sb4$ (10). 10 has been prepared in high yields from the reaction of 2e with Fe(CO)$\\sb5$ in the presence of Me$\\sb3$NO. Thermolysis of 10 gave 9, C$\\sb4$Me$\\sb4$S, and (C$\\sb5$Me$\\sb5)\\sb2$Rh$\\sb2(\\mu$-CO)($\\mu\\sb3$-S)Fe(CO)$\\sb3$ (11) in ca. 2:2:1 molar ratio. A double labeling thermolysis experiment shows that the Rh-C$\\sb4$Me$\\sb4$S fragment in 10 remains intact during its desulfurization.","Made available in DSpace on 2014-12-17T21:29:07Z (GMT). No. of bitstreams: 1 9329104.pdf: 6881346 bytes, checksum: 2888b89d8a39c9a5efe05312c79ab1a8 (MD5) Previous issue date: 1993","Embargo set by: Seth Robbins for item 72451 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","182 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1993."]},{"key":"dc:title","label":"Title","values":["Chemistry of Ruthenium and Rhodium Eta(4)-Thiophene Complexes"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Luo, Shifang"],"dc:date":["2014-12-17T21:29:07Z","10000-01-01","1993"],"dc:description":["Reduction of ($(\\eta\\sp6$-$\\rm C\\sb6Me\\sb6)Ru(\\eta\\sp5$-C$\\sb4$R$\\sb4$S)) (OTf)$\\sb2$(C$\\sb4$R$\\sb4$S = C$\\sb4$H$\\sb4$S (1a), 2,5-Me$\\sb2$C$\\sb4$H$\\sb2$S (1b), and 2,3,4,5-Me$\\sb4$C$\\sb4$S (1c)) and (($\\eta\\sp5$-C$\\sb4$Me$\\sb4$S)$\\sb2$Ru) (OTf)$\\sb2$ (1d) with Cp$\\sb2$Co produces (arene)Ru($\\eta\\sp4$-C$\\sb4$R$\\sb4$S) (2a-d). 2d is unstable $>-20\\sp\\circ$C. It reacts with Fe(CO)$\\sb5$ in the presence of Me$\\sb3$NO to yield the thermally stable $(\\eta\\sp5$-$\\rm C\\sb4Me\\sb4S)Ru(\\eta\\sp4{:}\\eta\\sp1$-$\\rm C\\sb4Me\\sb4S)Fe(CO)\\sb4$(2d$\\cdot$Fe(CO)$\\sb4).$","Thermolysis of (C$\\sb5$Me$\\sb5$)Rh($\\eta\\sp4$-C$\\sb4$Me$\\sb4$S) (2e) gives $(\\rm C\\sb5Me\\sb5)\\sb3Rh\\sb3 (\\eta\\sp4{:}\\eta\\sp1$-C$\\sb4$Me$\\sb4$S)$\\sb2$ (3) and C$\\sb4$Me$\\sb4$S. 3 further decomposes to give (C$\\sb5$Me$\\sb5)\\sb2$Rh$\\sb2$(C$\\sb4$Me$\\sb4$S) (4). Thermolysis of 2c in non-aromatic solvents such as hexane produces (C$\\sb6$Me$\\sb6)\\sb3$Ru$\\sb3$ $(\\eta\\sp4{:}\\eta\\sp1$-C$\\sb4$Me$\\sb4$S)$\\sb2$ (5a). In aromatic solvents, thermolysis of 2c yields the arene exchange products $(\\eta\\sp6$-solvent)(C$\\sb6$Me$\\sb6) \\sb2$Ru$\\sb3(\\eta\\sp4{:}\\eta\\sp1$-C$\\sb4$Me$\\sb4$S)$\\sb2$ (solvent = C$\\sb6$D$\\sb6$ (5b), toluene (5c)) at low concentrations while at high concentrations it yields both 5a and 5b (in C$\\sb6$D$\\sb6$) or 5c (in toluene). In the presence of H$\\sb2$, 2c decomposes to give (C$\\sb6$Me$\\sb6)\\sb2$Ru$\\sb2$ $(\\eta\\sp4{:}\\eta\\sp1$-C$\\sb4$Me$\\sb4$S)(H)$\\sb2$ (6).","Protonation of 2a-c with NH$\\sb4$PF$\\sb6$ affords (($\\eta\\sp6$-$\\rm C\\sb6Me\\sb6)Ru(\\eta\\sp4$-2-H-C$\\sb4$R$\\sb4$S)) PF$\\sb6$ (7a-c). The added proton is in the endo position of the carbon $\\alpha$ to sulfur. Protonation of 2d with NH$\\sb4$PF$\\sb6$ also affords the analogous ($(\\eta\\sp5$-C$\\sb5$Me$\\sb5$)Rh($\\eta\\sp4$-$2$ -H-C$\\sb4$Me$\\sb4$S)) PF$\\sb6$ (7d). Complex 7a undergoes C-S bond cleavage both in solution and the solid state to afford the thiapentadienyl complex (($\\eta\\sp6$-$\\rm C\\sb6Me\\sb6)Ru(\\eta\\sp5$-CH$\\sb2$=CH-CH=CH-S)) PF$\\sb6$ (8).","Complex 2e reacts with Fe$\\sb3$(CO)$\\sb $ to give (C$\\sb5$Me$\\sb5$)Rh$\\{\\eta\\sp5$-C$\\sb4$Me$\\sb4$Fe(CO)$\\sb3\\}$ (9) and (C$\\sb5$Me$\\sb5$)Rh($\\eta\\sp4$:$\\eta\\sp1$-C$\\sb4$Me$\\sb4$S)Fe(CO)$\\sb4$ (10). 10 has been prepared in high yields from the reaction of 2e with Fe(CO)$\\sb5$ in the presence of Me$\\sb3$NO. Thermolysis of 10 gave 9, C$\\sb4$Me$\\sb4$S, and (C$\\sb5$Me$\\sb5)\\sb2$Rh$\\sb2(\\mu$-CO)($\\mu\\sb3$-S)Fe(CO)$\\sb3$ (11) in ca. 2:2:1 molar ratio. A double labeling thermolysis experiment shows that the Rh-C$\\sb4$Me$\\sb4$S fragment in 10 remains intact during its desulfurization.","Made available in DSpace on 2014-12-17T21:29:07Z (GMT). No. of bitstreams: 1 9329104.pdf: 6881346 bytes, checksum: 2888b89d8a39c9a5efe05312c79ab1a8 (MD5) Previous issue date: 1993","Embargo set by: Seth Robbins for item 72451 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","182 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1993."],"dc:identifier":["http://hdl.handle.net/2142/72283","(UMI)AAI9329104"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Chemistry of Ruthenium and Rhodium Eta(4)-Thiophene Complexes"],"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":"2026-07-22T22:26:06Z"}