{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/19791"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/19791","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The addition of oxygen to coordinated thiophene","abstract":"The complex (Cp*Rh(TMT)) $\\sp{2+}$ (Cp* = $\\eta\\sp5$-C$\\sb5$Me$\\sb5$, TMT = tetramethylthiophene) can be reduced with two electrons to give the novel compound Cp*Rh(TMT), which features an $\\eta\\sp4$-bound tetramethylthiophene ligand with the sulfur atom oriented away from the metal center. The thiophenic sulfur atom in this complex is extremely nucleophilic, as shown by the reaction of Cp*Rh(TMT) with molecular oxygen, which cleanly yields the $\\eta\\sp4$-tetramethylthiophene-S-oxide complex, Cp*Rh(TMT-1-O).","abstract_html":"The complex (Cp*Rh(TMT)) $\\sp{2+}$ (Cp* = $\\eta\\sp5$-C$\\sb5$Me$\\sb5$, TMT = tetramethylthiophene) can be reduced with two electrons to give the novel compound Cp*Rh(TMT), which features an $\\eta\\sp4$-bound tetramethylthiophene ligand with the sulfur atom oriented away from the metal center. The thiophenic sulfur atom in this complex is extremely nucleophilic, as shown by the reaction of Cp*Rh(TMT) with molecular oxygen, which cleanly yields the $\\eta\\sp4$-tetramethylthiophene-S-oxide complex, Cp*Rh(TMT-1-O).","abstract_has_math":true,"creators":["Skaugset, Anton Eric"],"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":"2011-05-07T12:18:40Z","date_published":"2011-05-07T12:18:40Z","updated_at":"2026-07-22T22:25:14Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1992 Skaugset, Anton Eric"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9236595","(UMI)AAI9236595"],"render_values":[{"text":"AAI9236595","href":null,"code":true},{"text":"(UMI)AAI9236595","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/19791","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":["Skaugset, Anton Eric"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:18:40Z","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"]}]},{"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 Skaugset, Anton Eric"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9236595","(UMI)AAI9236595","http://hdl.handle.net/2142/19791"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The complex (Cp*Rh(TMT)) $\\sp{2+}$ (Cp* = $\\eta\\sp5$-C$\\sb5$Me$\\sb5$, TMT = tetramethylthiophene) can be reduced with two electrons to give the novel compound Cp*Rh(TMT), which features an $\\eta\\sp4$-bound tetramethylthiophene ligand with the sulfur atom oriented away from the metal center. The thiophenic sulfur atom in this complex is extremely nucleophilic, as shown by the reaction of Cp*Rh(TMT) with molecular oxygen, which cleanly yields the $\\eta\\sp4$-tetramethylthiophene-S-oxide complex, Cp*Rh(TMT-1-O).","When (Cp*Rh(TMT)) $\\sp{2+}$ is treated with three equivalents of hydroxide ion in aqueous solutions, a ring opened acetylpropenethiolate complex is isolated, Cp*Rh(Me$\\sb3$APT) (APT = acetylpropenethiolate) featuring an $\\eta\\sp4$-bound ligand which has a pendant acetyl group. Similar reactivity was observed for ((cymene)Ru(TMT)) $\\sp{2+}$, ((cymene)Ru(DMT)) $\\sp{2+}$ (DMT = dimethylthiophene), and ((TMT)$\\sb2$Ru) $\\sp{2+}$. In contrast, upon treatment with aqueous base, the complexes (Cp*Ir(TMT)) $\\sp{2+}$ and ((C$\\sb5$Me$\\sb4$H)Rh(TMT)) $\\sp{2+}$ yield tetramethylthiophene-1-oxide complexes. Base hydrolysis of ((cymene)Os(TMT)) $\\sp{2+}$ yields mixtures of the two products.","When the complex Cp*Rh(Me$\\sb3$APT) was treated with a single equivalent of H$\\sp+$, the 2-hydroxythiophenyl complex (Cp*Rh(TMT-2-OH)) $\\sp+$ was formed. The proposed mechanism for this recyclization invokes nucleophilic character for the terminal thiolate in the acetylpropenethiolate ligand. This reactivity is supported by the reaction of MeOTf with Cp*Rh(Me$\\sb3$APT), which yielded the S-Me adduct, (Cp*Rh(MeSC$\\sb3$Me$\\sb3$C(O)Me)) $\\sp+$.","The 2-hydroxythiophenyl complex was shown to be intermediate in the base hydrolysis of (Cp*Rh(TMT)) $\\sp{2+}$. The monoprotonation of (C$\\sb5$Me$\\sb4$H)Rh(TMT-1-O) also yielded the 2-hydroxythiophenyl complex. Upon addition of base, however, (C$\\sb5$Me$\\sb4$H)Rh(TMT-2-OH) did not reform the thiophene-1-oxide species, but rather yielded the acetylpropenethiolate complex, (C$\\sb5$Me$\\sb4$)Rh(Me$\\sb3$APT). This reactivity indicates that the initial attack of hydroxide at bound thiophene occurs at the sulfur atom, with competition occurring between deprotonation of the hydroxide (resulting in the thiophene-1-oxide complex) or migration of the hydroxide group to the $\\alpha$-carbon before deprotonation (resulting in the acetylpropenethiolate complex).","The complex Cp*Rh(Me$\\sb3$APT) undergoes facile and clean thermolysis to give tetramethylfuran and (Cp*$\\sb4$Rh$\\sb4$S$\\sb4$), a rhodium-sulfur cubane. The reaction is first order in concentration of Cp*Rh(Me$\\sb3$APT), and presence of phosphine does not affect the rate of the reaction.","Made available in DSpace on 2011-05-07T12:18:40Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9236595.pdf: 5802918 bytes, checksum: 59ef8a6ffa63e469e62aa22be7d81ad5 (MD5) Previous issue date: 1992","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:39:27Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:16:38-05:00 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 addition of oxygen to coordinated thiophene"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Skaugset, Anton Eric"],"dc:date":["2011-05-07T12:18:40Z","10000-01-01","1992"],"dc:description":["The complex (Cp*Rh(TMT)) $\\sp{2+}$ (Cp* = $\\eta\\sp5$-C$\\sb5$Me$\\sb5$, TMT = tetramethylthiophene) can be reduced with two electrons to give the novel compound Cp*Rh(TMT), which features an $\\eta\\sp4$-bound tetramethylthiophene ligand with the sulfur atom oriented away from the metal center. The thiophenic sulfur atom in this complex is extremely nucleophilic, as shown by the reaction of Cp*Rh(TMT) with molecular oxygen, which cleanly yields the $\\eta\\sp4$-tetramethylthiophene-S-oxide complex, Cp*Rh(TMT-1-O).","When (Cp*Rh(TMT)) $\\sp{2+}$ is treated with three equivalents of hydroxide ion in aqueous solutions, a ring opened acetylpropenethiolate complex is isolated, Cp*Rh(Me$\\sb3$APT) (APT = acetylpropenethiolate) featuring an $\\eta\\sp4$-bound ligand which has a pendant acetyl group. Similar reactivity was observed for ((cymene)Ru(TMT)) $\\sp{2+}$, ((cymene)Ru(DMT)) $\\sp{2+}$ (DMT = dimethylthiophene), and ((TMT)$\\sb2$Ru) $\\sp{2+}$. In contrast, upon treatment with aqueous base, the complexes (Cp*Ir(TMT)) $\\sp{2+}$ and ((C$\\sb5$Me$\\sb4$H)Rh(TMT)) $\\sp{2+}$ yield tetramethylthiophene-1-oxide complexes. Base hydrolysis of ((cymene)Os(TMT)) $\\sp{2+}$ yields mixtures of the two products.","When the complex Cp*Rh(Me$\\sb3$APT) was treated with a single equivalent of H$\\sp+$, the 2-hydroxythiophenyl complex (Cp*Rh(TMT-2-OH)) $\\sp+$ was formed. The proposed mechanism for this recyclization invokes nucleophilic character for the terminal thiolate in the acetylpropenethiolate ligand. This reactivity is supported by the reaction of MeOTf with Cp*Rh(Me$\\sb3$APT), which yielded the S-Me adduct, (Cp*Rh(MeSC$\\sb3$Me$\\sb3$C(O)Me)) $\\sp+$.","The 2-hydroxythiophenyl complex was shown to be intermediate in the base hydrolysis of (Cp*Rh(TMT)) $\\sp{2+}$. The monoprotonation of (C$\\sb5$Me$\\sb4$H)Rh(TMT-1-O) also yielded the 2-hydroxythiophenyl complex. Upon addition of base, however, (C$\\sb5$Me$\\sb4$H)Rh(TMT-2-OH) did not reform the thiophene-1-oxide species, but rather yielded the acetylpropenethiolate complex, (C$\\sb5$Me$\\sb4$)Rh(Me$\\sb3$APT). This reactivity indicates that the initial attack of hydroxide at bound thiophene occurs at the sulfur atom, with competition occurring between deprotonation of the hydroxide (resulting in the thiophene-1-oxide complex) or migration of the hydroxide group to the $\\alpha$-carbon before deprotonation (resulting in the acetylpropenethiolate complex).","The complex Cp*Rh(Me$\\sb3$APT) undergoes facile and clean thermolysis to give tetramethylfuran and (Cp*$\\sb4$Rh$\\sb4$S$\\sb4$), a rhodium-sulfur cubane. The reaction is first order in concentration of Cp*Rh(Me$\\sb3$APT), and presence of phosphine does not affect the rate of the reaction.","Made available in DSpace on 2011-05-07T12:18:40Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9236595.pdf: 5802918 bytes, checksum: 59ef8a6ffa63e469e62aa22be7d81ad5 (MD5) Previous issue date: 1992","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:39:27Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:16:38-05:00 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":["AAI9236595","(UMI)AAI9236595","http://hdl.handle.net/2142/19791"],"dc:language":["eng"],"dc:rights":["Copyright 1992 Skaugset, Anton Eric"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["The addition of oxygen to coordinated thiophene"],"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":"2026-07-22T22:25:14Z"}