{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/22734"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/22734","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Multinuclear NMR studies on solution structures and dynamics of triosmium hydrido carbonyl phosphine cluster compounds","abstract":"The reaction of ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(PPh$\\sb3$) with acetylene at room temperature provides two isomers of a hydridovinyl cluster. The solid-state structure of each isomer has been determined by single-crystal X-ray crystallography. The solution structures and dynamics have been studied by extensive $\\sp{13}$C NMR studies, including $\\sp{13}$C$\\{\\sp1$H$\\}$ COSY and $\\sp{13}$C spin saturation transfer experiments.","abstract_html":"The reaction of (<span class=\"etd-inline-math\">&mu;</span>-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(PPh$\\sb3$) with acetylene at room temperature provides two isomers of a hydridovinyl cluster. The solid-state structure of each isomer has been determined by single-crystal X-ray crystallography. The solution structures and dynamics have been studied by extensive $\\sp{13}$C NMR studies, including $\\sp{13}$C$\\{\\sp1$H$\\}$ COSY and $\\sp{13}$C spin saturation transfer experiments.","abstract_has_math":true,"creators":["Koike, Makoto"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Shapley, John R."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:49:42Z","date_published":"2011-05-07T13:49:42Z","updated_at":"2026-07-22T22:25:20Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1991 Koike, Makoto"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210874","(UMI)AAI9210874"],"render_values":[{"text":"AAI9210874","href":null,"code":true},{"text":"(UMI)AAI9210874","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/22734","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Shapley, John R."]},{"key":"dc:creator","label":"Author","values":["Koike, Makoto"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:49:42Z","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"]}]},{"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 Koike, Makoto"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210874","(UMI)AAI9210874","http://hdl.handle.net/2142/22734"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The reaction of ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(PPh$\\sb3$) with acetylene at room temperature provides two isomers of a hydridovinyl cluster. The solid-state structure of each isomer has been determined by single-crystal X-ray crystallography. The solution structures and dynamics have been studied by extensive $\\sp{13}$C NMR studies, including $\\sp{13}$C$\\{\\sp1$H$\\}$ COSY and $\\sp{13}$C spin saturation transfer experiments.","$\\sp1$H and $\\sp{13}$C NMR studies show that the reaction of ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(PPh$\\sb3$) with ethylene gives ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(PPh$\\sb3$)($\\mu$-CHCH$\\sb3$), instead of the previously formulated complex ($\\mu$-H)(H)Os$\\sb3$(CO)$\\sb9$(PPh$\\sb3$)(C$\\sb2$H$\\sb4$).","The reaction of ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(PMe$\\sb2$Ph) with Bu$\\sp{\\rm t}$NC produces two pairs of two isomers of an isonitrile cluster, ($\\mu$-H)(H)Os$\\sb3$(CO)$\\sb9$(PMe$\\sb2$Ph)(Bu$\\sp{\\rm t}$NC). The origin, structure, and dynamic behavior of these isomers have been investigated by $\\sp1$H, $\\sp{13}$C, and $\\sp{31}$P NMR studies.","The reaction of ($\\mu$-$\\rm H)\\sb2Os\\sb3(CO)\\sb9(PPh\\sb3$) with ethereal diazomethane in chloroform gives a novel compound, (($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb8$(PPh$\\sb3$)$\\sb2$) $\\sb2$($\\mu$-cis-CHCH=CHCH$\\sb2$CH), in which two triosmium carbonyl units are connected through a hydrocarbon fragment. This formulation is based on data obtained from mass spectrometry, elemental analysis, and extensive $\\sp1$H, $\\sp{13}$C, and $\\sp{31}$P NMR studies.","A combination of $\\sp{13}$C$\\{\\sp1$H$\\}$ COSY, selectively $\\sp1$H decoupled $\\sp{13}$C NMR, and $\\sp{13}$C spin saturation transfer experiments on the pair of tautomers, ($\\mu$-H)Os$\\sb3$(*CO)$\\sb{10}$($\\mu$-CH$\\sb3$)/($\\mu$-H)$\\sb2$Os$\\sb3$(*CO)$\\sb{10}$($\\mu$-CH$\\sb2$) has established the overall solution dynamics of these compounds.","Made available in DSpace on 2011-05-07T13:49:42Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210874.pdf: 5846032 bytes, checksum: cba627e4d2785e45f7fcb9c41677bbf0 (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:59:38Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:28:09-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","Author emailed IDEALS and requested open access. Restrictions lifted by kappleg@illinois.edu 2015-6-16.","Open"]},{"key":"dc:title","label":"Title","values":["Multinuclear NMR studies on solution structures and dynamics of triosmium hydrido carbonyl phosphine cluster compounds"]}]}],"canonical_facts":{"dc:contributor":["Shapley, John R."],"dc:creator":["Koike, Makoto"],"dc:date":["2011-05-07T13:49:42Z","1991"],"dc:description":["The reaction of ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(PPh$\\sb3$) with acetylene at room temperature provides two isomers of a hydridovinyl cluster. The solid-state structure of each isomer has been determined by single-crystal X-ray crystallography. The solution structures and dynamics have been studied by extensive $\\sp{13}$C NMR studies, including $\\sp{13}$C$\\{\\sp1$H$\\}$ COSY and $\\sp{13}$C spin saturation transfer experiments.","$\\sp1$H and $\\sp{13}$C NMR studies show that the reaction of ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(PPh$\\sb3$) with ethylene gives ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(PPh$\\sb3$)($\\mu$-CHCH$\\sb3$), instead of the previously formulated complex ($\\mu$-H)(H)Os$\\sb3$(CO)$\\sb9$(PPh$\\sb3$)(C$\\sb2$H$\\sb4$).","The reaction of ($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb9$(PMe$\\sb2$Ph) with Bu$\\sp{\\rm t}$NC produces two pairs of two isomers of an isonitrile cluster, ($\\mu$-H)(H)Os$\\sb3$(CO)$\\sb9$(PMe$\\sb2$Ph)(Bu$\\sp{\\rm t}$NC). The origin, structure, and dynamic behavior of these isomers have been investigated by $\\sp1$H, $\\sp{13}$C, and $\\sp{31}$P NMR studies.","The reaction of ($\\mu$-$\\rm H)\\sb2Os\\sb3(CO)\\sb9(PPh\\sb3$) with ethereal diazomethane in chloroform gives a novel compound, (($\\mu$-H)$\\sb2$Os$\\sb3$(CO)$\\sb8$(PPh$\\sb3$)$\\sb2$) $\\sb2$($\\mu$-cis-CHCH=CHCH$\\sb2$CH), in which two triosmium carbonyl units are connected through a hydrocarbon fragment. This formulation is based on data obtained from mass spectrometry, elemental analysis, and extensive $\\sp1$H, $\\sp{13}$C, and $\\sp{31}$P NMR studies.","A combination of $\\sp{13}$C$\\{\\sp1$H$\\}$ COSY, selectively $\\sp1$H decoupled $\\sp{13}$C NMR, and $\\sp{13}$C spin saturation transfer experiments on the pair of tautomers, ($\\mu$-H)Os$\\sb3$(*CO)$\\sb{10}$($\\mu$-CH$\\sb3$)/($\\mu$-H)$\\sb2$Os$\\sb3$(*CO)$\\sb{10}$($\\mu$-CH$\\sb2$) has established the overall solution dynamics of these compounds.","Made available in DSpace on 2011-05-07T13:49:42Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210874.pdf: 5846032 bytes, checksum: cba627e4d2785e45f7fcb9c41677bbf0 (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:59:38Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:28:09-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","Author emailed IDEALS and requested open access. Restrictions lifted by kappleg@illinois.edu 2015-6-16.","Open"],"dc:identifier":["AAI9210874","(UMI)AAI9210874","http://hdl.handle.net/2142/22734"],"dc:language":["eng"],"dc:rights":["Copyright 1991 Koike, Makoto"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Multinuclear NMR studies on solution structures and dynamics of triosmium hydrido carbonyl phosphine 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"}