{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/20352"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/20352","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis and reactivity of organometallic nitridoosmium(VI), ruthenium(VI) complexes","abstract":"New organometallic osmium(VI) complexes with sulfur and oxygen containing ligands, (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$Y) $\\sp-$ $\\{$Y = (SCH$\\sb2$CH$\\sb2$S), (SCN)$\\sb2$, (S), (S-C$\\sb5$H$\\sb4$N), (WS$\\sb4$), (MoS$\\sb4$), (SO$\\sb4$), (CO$\\sb3$), (ReO$\\sb4)\\sb2\\}$ were prepared. Two crystal structures of (Os(N)(R)$\\sb2$(SC$\\sb5$H$\\sb4$N)) $\\sb2$, (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(R)$\\sb2$(WS$\\sb4$)) (R = CH$\\sb2$SiMe$\\sb3)$ were determined.","abstract_html":"New organometallic osmium(VI) complexes with sulfur and oxygen containing ligands, (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$Y) $\\sp-$ $\\{$Y = (SCH$\\sb2$CH$\\sb2$S), (SCN)$\\sb2$, (S), (S-C$\\sb5$H$\\sb4$N), (WS$\\sb4$), (MoS$\\sb4$), (SO$\\sb4$), (CO$\\sb3$), (ReO$\\sb4)\\sb2\\}$ were prepared. Two crystal structures of (Os(N)(R)$\\sb2$(SC$\\sb5$H$\\sb4$N)) $\\sb2$, (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(R)$\\sb2$(WS$\\sb4$)) (R = CH$\\sb2$SiMe$\\sb3)$ were determined.","abstract_has_math":true,"creators":["Zhang, Naijie"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Shapley, Patricia A."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T12:36:46Z","date_published":"2011-05-07T12:36:46Z","updated_at":"2026-07-22T22:25:15Z","subjects":["Chemistry, Inorganic","Chemistry, Organic"],"languages":["eng"],"rights":["Copyright 1991 Zhang, Naijie"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9211056","(UMI)AAI9211056"],"render_values":[{"text":"AAI9211056","href":null,"code":true},{"text":"(UMI)AAI9211056","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/20352","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Shapley, Patricia A."]},{"key":"dc:creator","label":"Author","values":["Zhang, Naijie"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:36:46Z","10000-01-01","1991"]},{"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","Chemistry, Organic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1991 Zhang, Naijie"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9211056","(UMI)AAI9211056","http://hdl.handle.net/2142/20352"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["New organometallic osmium(VI) complexes with sulfur and oxygen containing ligands, (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$Y) $\\sp-$ $\\{$Y = (SCH$\\sb2$CH$\\sb2$S), (SCN)$\\sb2$, (S), (S-C$\\sb5$H$\\sb4$N), (WS$\\sb4$), (MoS$\\sb4$), (SO$\\sb4$), (CO$\\sb3$), (ReO$\\sb4)\\sb2\\}$ were prepared. Two crystal structures of (Os(N)(R)$\\sb2$(SC$\\sb5$H$\\sb4$N)) $\\sb2$, (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(R)$\\sb2$(WS$\\sb4$)) (R = CH$\\sb2$SiMe$\\sb3)$ were determined.","The first osmium and ruthenium alkyl complexes containing bidentate chromate group (NBu$\\sp{\\rm n}\\sb4$) (M(N)(CH$\\sb2$SiME$\\sb3)\\sb2$(CrO$\\sb4$)) (M = Os, Ru) were synthesized by the reaction of (M(N)R$\\sb2$Cl$\\sb2$) $\\sp-$ with Ag$\\sb2$CrO$\\sb4$ or K$\\sb2$CO$\\sb4$ in high yields. A crystal structure of (NBu$\\sp{\\rm n}\\sb4$) (Ru(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$(CrO$\\sb4$)) was determined. All of the osmium and ruthenium complexes are thermally stable to air and water and soluble in organic solvents.","The osmium and ruthenium chromate complexes, cis- (NBu$\\sp{\\rm n}\\sb4$) (M(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$CrO$\\sb4$) (M = Ru, Os) are catalysts for selective oxidation of alcohols to the corresponding carbonyl compounds under mild conditions with molecular oxygen as a secondary oxidant. Kinetic and mechanistic studies were carried out on the oxidation of benzyl alcohol by cis- (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$CrO$\\sb4$). The reaction is first order in both cis- (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$CrO$\\sb4$) and O$\\sb2$ and zero order in alcohol. Dioxygen labelling studies show that the $\\sp{17}$O$\\sb2$is incorporated into the bridge oxo of cis- (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$CrO$\\sb4$). The most likely mechanism for the oxidation of alcohols by cis- (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$CrO$\\sb4$) involves a concentrated $\\beta$-hydrogen elimination and oxygen insertion as a rate-determining step.","Made available in DSpace on 2011-05-07T12:36:46Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9211056.pdf: 5681368 bytes, checksum: ec3a8382494897e4427a02aa277e00a1 (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:43:19Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:56-05:00 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":["Synthesis and reactivity of organometallic nitridoosmium(VI), ruthenium(VI) complexes"]}]}],"canonical_facts":{"dc:contributor":["Shapley, Patricia A."],"dc:creator":["Zhang, Naijie"],"dc:date":["2011-05-07T12:36:46Z","10000-01-01","1991"],"dc:description":["New organometallic osmium(VI) complexes with sulfur and oxygen containing ligands, (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$Y) $\\sp-$ $\\{$Y = (SCH$\\sb2$CH$\\sb2$S), (SCN)$\\sb2$, (S), (S-C$\\sb5$H$\\sb4$N), (WS$\\sb4$), (MoS$\\sb4$), (SO$\\sb4$), (CO$\\sb3$), (ReO$\\sb4)\\sb2\\}$ were prepared. Two crystal structures of (Os(N)(R)$\\sb2$(SC$\\sb5$H$\\sb4$N)) $\\sb2$, (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(R)$\\sb2$(WS$\\sb4$)) (R = CH$\\sb2$SiMe$\\sb3)$ were determined.","The first osmium and ruthenium alkyl complexes containing bidentate chromate group (NBu$\\sp{\\rm n}\\sb4$) (M(N)(CH$\\sb2$SiME$\\sb3)\\sb2$(CrO$\\sb4$)) (M = Os, Ru) were synthesized by the reaction of (M(N)R$\\sb2$Cl$\\sb2$) $\\sp-$ with Ag$\\sb2$CrO$\\sb4$ or K$\\sb2$CO$\\sb4$ in high yields. A crystal structure of (NBu$\\sp{\\rm n}\\sb4$) (Ru(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$(CrO$\\sb4$)) was determined. All of the osmium and ruthenium complexes are thermally stable to air and water and soluble in organic solvents.","The osmium and ruthenium chromate complexes, cis- (NBu$\\sp{\\rm n}\\sb4$) (M(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$CrO$\\sb4$) (M = Ru, Os) are catalysts for selective oxidation of alcohols to the corresponding carbonyl compounds under mild conditions with molecular oxygen as a secondary oxidant. Kinetic and mechanistic studies were carried out on the oxidation of benzyl alcohol by cis- (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$CrO$\\sb4$). The reaction is first order in both cis- (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$CrO$\\sb4$) and O$\\sb2$ and zero order in alcohol. Dioxygen labelling studies show that the $\\sp{17}$O$\\sb2$is incorporated into the bridge oxo of cis- (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$CrO$\\sb4$). The most likely mechanism for the oxidation of alcohols by cis- (NBu$\\sp{\\rm n}\\sb4$) (Os(N)(CH$\\sb2$SiMe$\\sb3)\\sb2$CrO$\\sb4$) involves a concentrated $\\beta$-hydrogen elimination and oxygen insertion as a rate-determining step.","Made available in DSpace on 2011-05-07T12:36:46Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9211056.pdf: 5681368 bytes, checksum: ec3a8382494897e4427a02aa277e00a1 (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:43:19Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:56-05:00 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":["AAI9211056","(UMI)AAI9211056","http://hdl.handle.net/2142/20352"],"dc:language":["eng"],"dc:rights":["Copyright 1991 Zhang, Naijie"],"dc:subject":["Chemistry, Inorganic","Chemistry, Organic"],"dc:title":["Synthesis and reactivity of organometallic nitridoosmium(VI), ruthenium(VI) 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":"2026-07-22T22:25:15Z"}