{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/22589"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/22589","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Oxyligands in triosmium carbonyl cluster compounds","abstract":"Tridentate triply bridging phosphonate and arsonate clusters of the general formula ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$($\\mu\\sb3$, $\\eta\\sp3$-O$\\sb3$ER) (E = P, R = Ph (1), Me; E = As, R = Ph) were prepared. The reaction scheme involved (1) generation of a solution containing a labile cluster species by reaction of H$\\sb3$Os$\\sb3$(CO)$\\sb9$CH with neat trifluoromethanesulfonic (triflic) acid, (2) addition of a large excess of the appropriate free acid, and (3) water quench. A diffraction study of 1 showed the capping PhPO$\\sb3$ ligand in a triply bridging tridentate coordination mode. Compound 1 is fluxional, and hydride migration was established as the low barrier dynamic process. Solid/solution structure equivalence for this class of clusters was demonstrated.","abstract_html":"Tridentate triply bridging phosphonate and arsonate clusters of the general formula (<span class=\"etd-inline-math\">&mu;</span>-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(<span class=\"etd-inline-math\">&mu;\\sb3</span>, $\\eta\\sp3$-O$\\sb3$ER) (E = P, R = Ph (1), Me; E = As, R = Ph) were prepared. The reaction scheme involved (1) generation of a solution containing a labile cluster species by reaction of H$\\sb3$Os$\\sb3$(CO)$\\sb9$CH with neat trifluoromethanesulfonic (triflic) acid, (2) addition of a large excess of the appropriate free acid, and (3) water quench. A diffraction study of 1 showed the capping PhPO$\\sb3$ ligand in a triply bridging tridentate coordination mode. Compound 1 is fluxional, and hydride migration was established as the low barrier dynamic process. Solid/solution structure equivalence for this class of clusters was demonstrated.","abstract_has_math":true,"creators":["Frauenhoff, Greg Robert"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Klemperer, Walter G."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:44:44Z","date_published":"2011-05-07T13:44:44Z","updated_at":"2026-07-22T22:25:20Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1989 Frauenhoff, Greg Robert"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI8916246","(UMI)AAI8916246"],"render_values":[{"text":"AAI8916246","href":null,"code":true},{"text":"(UMI)AAI8916246","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/22589","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Klemperer, Walter G."]},{"key":"dc:creator","label":"Author","values":["Frauenhoff, Greg Robert"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:44:44Z","10000-01-01","1989"]},{"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 1989 Frauenhoff, Greg Robert"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI8916246","(UMI)AAI8916246","http://hdl.handle.net/2142/22589"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Tridentate triply bridging phosphonate and arsonate clusters of the general formula ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$($\\mu\\sb3$, $\\eta\\sp3$-O$\\sb3$ER) (E = P, R = Ph (1), Me; E = As, R = Ph) were prepared. The reaction scheme involved (1) generation of a solution containing a labile cluster species by reaction of H$\\sb3$Os$\\sb3$(CO)$\\sb9$CH with neat trifluoromethanesulfonic (triflic) acid, (2) addition of a large excess of the appropriate free acid, and (3) water quench. A diffraction study of 1 showed the capping PhPO$\\sb3$ ligand in a triply bridging tridentate coordination mode. Compound 1 is fluxional, and hydride migration was established as the low barrier dynamic process. Solid/solution structure equivalence for this class of clusters was demonstrated.","The bis triflate cluster H$\\sb2$Os$\\sb3$(CO)$\\sb9$(O$\\sb3$SCF$\\sb3$) was isolated (76% yield) from the triflic acid/H$\\sb3$Os$\\sb3$(CO)$\\sb9$CH solution. It reacts with neat carboxylic acids to give clusters of the general formula ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$($\\mu$, $\\eta\\sp2$-O$\\sb2$CR)($\\eta\\sp1$-O$\\sb2$CR) (R = H, CF$\\sb3$) and ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$($\\mu$, $\\eta\\sp2$-O$\\sb2$CR) ($\\eta\\sp1$-O$\\sb3$SCF$\\sb3$) (R = H, CH$\\sb3$, CF$\\sb3$). A diffraction study of ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$($\\mu,\\ \\eta\\sp2$-O$\\sb2$CCH$\\sb3$)($\\eta\\sp1$-O$\\sb3$SCF$\\sb3$) showed the oxyligands in the trans axial configuration. This compound was found to be unreactive towards a variety of potential ligands (e.g. THF, NCCF$\\sb3$, CO). It did react with halides and thiosulfate to give HOs$\\sb3$(CO)$\\sb{10}$X derivatives and H$\\sb2$Os$\\sb3$(CO)$\\sb9$($\\mu\\sb3$-S) respectively. Reaction of H$\\sb2$Os$\\sb3$(CO)$\\sb9$(O$\\sb3$SCF$\\sb3)\\sb2$ with acetonitrile gave (($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(NCCH$\\sb3)\\sb3$) (O$\\sb3$SCF$\\sb3$) $\\sb2$. This cluster exists as isomers at low temperature ($-30\\sp\\circ$C). These isomers interconvert by hydride migration.","Os$\\sb3$(CO)$\\sb{12}$ chemisorbed to silica has been examined by magic-angle-spinning $\\sp{13}$C NMR, and the structure of the chemisorbed species identified as ($\\mu$-H)Os$\\sb3$(CO)$\\sb9$($\\mu$-OSi=) by comparison with model compounds. Molecular models, such as ($\\mu$-H)Os$\\sb3$(CO)$\\sb{11}(\\eta\\sp1$-O$\\sb2$CCF$\\sb3$), for possible intermediates in the chemisorption reaction were prepared.","Made available in DSpace on 2011-05-07T13:44:44Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 8916246.pdf: 6942590 bytes, checksum: ed9b037f9b10964275dcca24eb822c81 (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:58:39Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:27:36-05:00 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":["Oxyligands in triosmium carbonyl cluster compounds"]}]}],"canonical_facts":{"dc:contributor":["Klemperer, Walter G."],"dc:creator":["Frauenhoff, Greg Robert"],"dc:date":["2011-05-07T13:44:44Z","10000-01-01","1989"],"dc:description":["Tridentate triply bridging phosphonate and arsonate clusters of the general formula ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$($\\mu\\sb3$, $\\eta\\sp3$-O$\\sb3$ER) (E = P, R = Ph (1), Me; E = As, R = Ph) were prepared. The reaction scheme involved (1) generation of a solution containing a labile cluster species by reaction of H$\\sb3$Os$\\sb3$(CO)$\\sb9$CH with neat trifluoromethanesulfonic (triflic) acid, (2) addition of a large excess of the appropriate free acid, and (3) water quench. A diffraction study of 1 showed the capping PhPO$\\sb3$ ligand in a triply bridging tridentate coordination mode. Compound 1 is fluxional, and hydride migration was established as the low barrier dynamic process. Solid/solution structure equivalence for this class of clusters was demonstrated.","The bis triflate cluster H$\\sb2$Os$\\sb3$(CO)$\\sb9$(O$\\sb3$SCF$\\sb3$) was isolated (76% yield) from the triflic acid/H$\\sb3$Os$\\sb3$(CO)$\\sb9$CH solution. It reacts with neat carboxylic acids to give clusters of the general formula ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$($\\mu$, $\\eta\\sp2$-O$\\sb2$CR)($\\eta\\sp1$-O$\\sb2$CR) (R = H, CF$\\sb3$) and ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$($\\mu$, $\\eta\\sp2$-O$\\sb2$CR) ($\\eta\\sp1$-O$\\sb3$SCF$\\sb3$) (R = H, CH$\\sb3$, CF$\\sb3$). A diffraction study of ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$($\\mu,\\ \\eta\\sp2$-O$\\sb2$CCH$\\sb3$)($\\eta\\sp1$-O$\\sb3$SCF$\\sb3$) showed the oxyligands in the trans axial configuration. This compound was found to be unreactive towards a variety of potential ligands (e.g. THF, NCCF$\\sb3$, CO). It did react with halides and thiosulfate to give HOs$\\sb3$(CO)$\\sb{10}$X derivatives and H$\\sb2$Os$\\sb3$(CO)$\\sb9$($\\mu\\sb3$-S) respectively. Reaction of H$\\sb2$Os$\\sb3$(CO)$\\sb9$(O$\\sb3$SCF$\\sb3)\\sb2$ with acetonitrile gave (($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(NCCH$\\sb3)\\sb3$) (O$\\sb3$SCF$\\sb3$) $\\sb2$. This cluster exists as isomers at low temperature ($-30\\sp\\circ$C). These isomers interconvert by hydride migration.","Os$\\sb3$(CO)$\\sb{12}$ chemisorbed to silica has been examined by magic-angle-spinning $\\sp{13}$C NMR, and the structure of the chemisorbed species identified as ($\\mu$-H)Os$\\sb3$(CO)$\\sb9$($\\mu$-OSi=) by comparison with model compounds. Molecular models, such as ($\\mu$-H)Os$\\sb3$(CO)$\\sb{11}(\\eta\\sp1$-O$\\sb2$CCF$\\sb3$), for possible intermediates in the chemisorption reaction were prepared.","Made available in DSpace on 2011-05-07T13:44:44Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 8916246.pdf: 6942590 bytes, checksum: ed9b037f9b10964275dcca24eb822c81 (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:58:39Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:27:36-05:00 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":["AAI8916246","(UMI)AAI8916246","http://hdl.handle.net/2142/22589"],"dc:language":["eng"],"dc:rights":["Copyright 1989 Frauenhoff, Greg Robert"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Oxyligands in triosmium carbonyl cluster compounds"],"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":"2026-07-22T22:25:20Z"}