{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/23004"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/23004","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis and reactivity studies of rhenium carbido carbonyl cluster compounds","abstract":"Made available in DSpace on 2011-05-07T13:58:44Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9512401.pdf: 4691506 bytes, checksum: 02c1a3070ddaa3bd747f6be4bbb8dc6f (MD5) Previous issue date: 1994","abstract_html":"Made available in DSpace on 2011-05-07T13:58:44Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9512401.pdf: 4691506 bytes, checksum: 02c1a3070ddaa3bd747f6be4bbb8dc6f (MD5) Previous issue date: 1994","abstract_has_math":false,"creators":["Hsu, Gishun"],"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":"2011-05-07T13:58:44Z","date_published":"2011-05-07T13:58:44Z","updated_at":"2026-07-22T22:25:21Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1994 Hsu, Gishun"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9512401","(UMI)AAI9512401"],"render_values":[{"text":"AAI9512401","href":null,"code":true},{"text":"(UMI)AAI9512401","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/23004","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":["Hsu, Gishun"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:58:44Z","10000-01-01","1994"]},{"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 1994 Hsu, Gishun"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9512401","(UMI)AAI9512401","http://hdl.handle.net/2142/23004"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Made available in DSpace on 2011-05-07T13:58:44Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9512401.pdf: 4691506 bytes, checksum: 02c1a3070ddaa3bd747f6be4bbb8dc6f (MD5) Previous issue date: 1994","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:01:31Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:29:11-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","Treatment of $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack\\sp{3-}$ with PPh$\\sb3$ in the presence of two equivalents of $\\rm\\lbrack Cp\\sb2Fe\\rbrack\\sp+$ under a CO atmosphere provided $\\rm\\lbrack Re\\sb6C(CO)\\sb{19}\\rbrack\\sp{2-}$. X-ray diffractional studies and $\\sp{13}$C NMR studies on $\\rm\\lbrack Re\\sb6C(CO)\\sb{19}\\rbrack\\sp{2-}$ showed a congested ligand environment. Sunlamp irradiation of $\\rm\\lbrack Re\\sb6C(CO)\\sb{19}\\rbrack\\sp{2-}$ in the presence of H$\\sb2$ gave $\\rm\\lbrack H\\sb2Re\\sb6C(CO)\\sb{18}\\rbrack\\sp{2-}$.","Treatment of $\\rm \\lbrack PPN\\rbrack\\sb3\\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack$ with two equivalents of $\\rm\\lbrack Cp\\sb2Fe\\rbrack\\sp+$ in the presence of diazomethane gave (PPN) (Re$\\sb7$C(CO)$\\sb{21}$(CH$\\sb2$)). Treatment of $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}(CH\\sb2)\\rbrack\\sp-$ with acetonitrile gave $\\rm\\lbrack Re\\sb6C(CO)\\sb{18}(CH\\sb2)\\rbrack\\sp{2-}$. The methylene ligand in $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}(CH\\sb2)\\rbrack$ and $\\rm\\lbrack Re\\sb6C(CO)\\sb{18}(CH\\sb2)\\rbrack\\sp{2-}$ is found bridging a rhenium-rhenium edge. The syntheses of other $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}L\\rbrack\\sp-$ and $\\rm \\lbrack Re\\sb6C(CO)\\sb{18}L\\rbrack\\sp{2-}$ compounds are also discussed.","The reaction of $\\rm\\lbrack PPN\\rbrack\\sb2\\lbrack Re\\sb6C(CO)\\sb{19}\\rbrack$ with Mo(CO)$\\sb6$ and $\\rm Ru\\sb3(CO)\\sb{12}$ under photolytic conditions gave $\\rm \\lbrack PPN\\rbrack\\sb2\\lbrack Re\\sb6C(CO)\\sb{18}Mo(CO)\\sb4\\rbrack$ and $\\rm \\lbrack PPN\\rbrack\\sb2\\lbrack Re\\sb6C(CO)\\sb{18}Ru(CO)\\sb3\\rbrack$, respectively. A comparison of the physical properties and reactivity of $\\rm \\lbrack PPN\\rbrack\\sb2\\lbrack Re\\sb6C(CO)\\sb{18}Mo(CO)\\sb4\\rbrack$ and $\\rm\\lbrack PPN\\rbrack\\sb2\\lbrack Re\\sb6C(CO)\\sb{18}Ru(CO)\\sb3\\rbrack$ is described.","The reaction of either $\\rm\\lbrack H\\sb2Re\\sb6C(CO)\\sb{18}\\rbrack\\sp{2-}$ or $\\rm\\lbrack HRe\\sb6C(CO)\\sb{18}\\rbrack\\sp{3-}$ with (AuPPh$\\sb3$)Cl in the presence of DBU gave $\\rm\\lbrack Re\\sb6C(CO)\\sb{18}(AuPPh\\sb3)\\sb2\\rbrack\\sp{2-}$. $\\rm\\lbrack Re\\sb6C(CO)\\sb{18}(AuPPh\\sb3)\\sb2\\rbrack\\sp{2-}$ reacted with (AuPPh$\\sb3$)NO$\\sb3$ to give $\\rm\\lbrack Re\\sb6C(CO)\\sb{18}(AuPPh\\sb3)\\sb4\\rbrack$. $\\rm \\lbrack Re\\sb6C(CO)\\sb{18}(AuPPh\\sb3)\\sb2\\rbrack\\sp{2-}$ also reacted with $\\rm\\lbrack Rh(CO)\\sb2Cl\\rbrack\\sb2$ to give $\\rm \\lbrack Re\\sb6C(CO)\\sb{18}(AuPPh\\sb3)\\sb2Rh(CO)\\sb2\\rbrack\\sp-$. Synthesis of other $\\rm \\lbrack Re\\sb6C(CO)\\sb{18}ML\\sb{n}\\rbrack\\sp{3-}$ complexes will also be discussed.","Treatment of $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack\\sp{3-}$ with one equivalent of $\\rm\\lbrack Cp\\sb2Fe\\rbrack\\sp+$ gave the $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack\\sp{2-}$ radical, and introduction of tributyltin hydride or a silane gave $\\rm\\lbrack HRe\\sb7C(CO)\\sb{21}\\rbrack\\sp{2-}$. The $\\rm \\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack\\sp{2-}$ radical also reacted with solvents such as acetone or THF, giving $\\rm\\lbrack HRe\\sb7C(CO)\\sb{21}\\rbrack\\sp{2-}$. The nature of the counter ion in the cluster compound and the $\\rm\\lbrack Cp\\sb2Fe\\rbrack\\sp+$ oxidant also played a role in the reactivity.","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Synthesis and reactivity studies of rhenium carbido carbonyl cluster compounds"]}]}],"canonical_facts":{"dc:contributor":["Shapley, John R."],"dc:creator":["Hsu, Gishun"],"dc:date":["2011-05-07T13:58:44Z","10000-01-01","1994"],"dc:description":["Made available in DSpace on 2011-05-07T13:58:44Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9512401.pdf: 4691506 bytes, checksum: 02c1a3070ddaa3bd747f6be4bbb8dc6f (MD5) Previous issue date: 1994","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:01:31Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:29:11-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","Treatment of $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack\\sp{3-}$ with PPh$\\sb3$ in the presence of two equivalents of $\\rm\\lbrack Cp\\sb2Fe\\rbrack\\sp+$ under a CO atmosphere provided $\\rm\\lbrack Re\\sb6C(CO)\\sb{19}\\rbrack\\sp{2-}$. X-ray diffractional studies and $\\sp{13}$C NMR studies on $\\rm\\lbrack Re\\sb6C(CO)\\sb{19}\\rbrack\\sp{2-}$ showed a congested ligand environment. Sunlamp irradiation of $\\rm\\lbrack Re\\sb6C(CO)\\sb{19}\\rbrack\\sp{2-}$ in the presence of H$\\sb2$ gave $\\rm\\lbrack H\\sb2Re\\sb6C(CO)\\sb{18}\\rbrack\\sp{2-}$.","Treatment of $\\rm \\lbrack PPN\\rbrack\\sb3\\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack$ with two equivalents of $\\rm\\lbrack Cp\\sb2Fe\\rbrack\\sp+$ in the presence of diazomethane gave (PPN) (Re$\\sb7$C(CO)$\\sb{21}$(CH$\\sb2$)). Treatment of $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}(CH\\sb2)\\rbrack\\sp-$ with acetonitrile gave $\\rm\\lbrack Re\\sb6C(CO)\\sb{18}(CH\\sb2)\\rbrack\\sp{2-}$. The methylene ligand in $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}(CH\\sb2)\\rbrack$ and $\\rm\\lbrack Re\\sb6C(CO)\\sb{18}(CH\\sb2)\\rbrack\\sp{2-}$ is found bridging a rhenium-rhenium edge. The syntheses of other $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}L\\rbrack\\sp-$ and $\\rm \\lbrack Re\\sb6C(CO)\\sb{18}L\\rbrack\\sp{2-}$ compounds are also discussed.","The reaction of $\\rm\\lbrack PPN\\rbrack\\sb2\\lbrack Re\\sb6C(CO)\\sb{19}\\rbrack$ with Mo(CO)$\\sb6$ and $\\rm Ru\\sb3(CO)\\sb{12}$ under photolytic conditions gave $\\rm \\lbrack PPN\\rbrack\\sb2\\lbrack Re\\sb6C(CO)\\sb{18}Mo(CO)\\sb4\\rbrack$ and $\\rm \\lbrack PPN\\rbrack\\sb2\\lbrack Re\\sb6C(CO)\\sb{18}Ru(CO)\\sb3\\rbrack$, respectively. A comparison of the physical properties and reactivity of $\\rm \\lbrack PPN\\rbrack\\sb2\\lbrack Re\\sb6C(CO)\\sb{18}Mo(CO)\\sb4\\rbrack$ and $\\rm\\lbrack PPN\\rbrack\\sb2\\lbrack Re\\sb6C(CO)\\sb{18}Ru(CO)\\sb3\\rbrack$ is described.","The reaction of either $\\rm\\lbrack H\\sb2Re\\sb6C(CO)\\sb{18}\\rbrack\\sp{2-}$ or $\\rm\\lbrack HRe\\sb6C(CO)\\sb{18}\\rbrack\\sp{3-}$ with (AuPPh$\\sb3$)Cl in the presence of DBU gave $\\rm\\lbrack Re\\sb6C(CO)\\sb{18}(AuPPh\\sb3)\\sb2\\rbrack\\sp{2-}$. $\\rm\\lbrack Re\\sb6C(CO)\\sb{18}(AuPPh\\sb3)\\sb2\\rbrack\\sp{2-}$ reacted with (AuPPh$\\sb3$)NO$\\sb3$ to give $\\rm\\lbrack Re\\sb6C(CO)\\sb{18}(AuPPh\\sb3)\\sb4\\rbrack$. $\\rm \\lbrack Re\\sb6C(CO)\\sb{18}(AuPPh\\sb3)\\sb2\\rbrack\\sp{2-}$ also reacted with $\\rm\\lbrack Rh(CO)\\sb2Cl\\rbrack\\sb2$ to give $\\rm \\lbrack Re\\sb6C(CO)\\sb{18}(AuPPh\\sb3)\\sb2Rh(CO)\\sb2\\rbrack\\sp-$. Synthesis of other $\\rm \\lbrack Re\\sb6C(CO)\\sb{18}ML\\sb{n}\\rbrack\\sp{3-}$ complexes will also be discussed.","Treatment of $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack\\sp{3-}$ with one equivalent of $\\rm\\lbrack Cp\\sb2Fe\\rbrack\\sp+$ gave the $\\rm\\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack\\sp{2-}$ radical, and introduction of tributyltin hydride or a silane gave $\\rm\\lbrack HRe\\sb7C(CO)\\sb{21}\\rbrack\\sp{2-}$. The $\\rm \\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack\\sp{2-}$ radical also reacted with solvents such as acetone or THF, giving $\\rm\\lbrack HRe\\sb7C(CO)\\sb{21}\\rbrack\\sp{2-}$. The nature of the counter ion in the cluster compound and the $\\rm\\lbrack Cp\\sb2Fe\\rbrack\\sp+$ oxidant also played a role in the reactivity.","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9512401","(UMI)AAI9512401","http://hdl.handle.net/2142/23004"],"dc:language":["eng"],"dc:rights":["Copyright 1994 Hsu, Gishun"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Synthesis and reactivity studies of rhenium carbido 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":"2026-07-22T22:25:21Z"}