{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/22793"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/22793","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 high-nuclearity carbido carbonyl clusters of heptarhenium-iridium and decaruthenium","abstract":"The cluster anion ($\\rm Re\\sb7C(CO)\\sb{21}Ir(C\\sb8H\\sb{14})(CO)\\rbrack \\sp{2-}$ has been synthesized by the capping of ($\\rm Re\\sb7C(CO)\\sb{21}\\rbrack \\sp{3-}$ with the in-situ generated cationic species from the reaction of ($\\rm Ir(C\\sb8H\\sb{14})\\sb2(CO)Cl\\rbrack \\sb2$ and AgBF$\\sb4.$ This new heptarhenium-iridium compound reacts with two electron donors to give ligand-substituted compounds ($\\rm Re\\sb7C(CO)\\sb{21}Ir(L)(CO)\\rbrack \\sp{2-}$ (L = CO, $\\rm C\\sb2H\\sb4,$ PMePh$\\sb2,$ and PPh$\\sb3),$ and with triphenylsilane and allyl bromide to form the oxidative addition products ($\\rm Re\\sb7C(CO)\\sb{21}Ir(H)(CO)(SiPh\\sb3)\\rbrack \\sp{2-}$ and ($\\rm Re\\sb7C(CO)\\sb{21}Ir(\\eta\\sp3C\\sb3H\\sb5)(CO)\\rbrack \\sp-.$ The reactivities at iridium parallel those of the indenyl complex $\\rm (\\eta\\sp5C\\sb9H\\sb7)Ir(C\\sb8H\\sb{14})(CO),$ thus giving further support for the previously proposed analogy between ($\\rm Re\\sb7C(CO)\\sb{21}\\rbrack \\sp{3-}$ and the cyclopentadienyl ligand and its derivatives. Formulation and characterization of these new compounds are based on elemental analysis, IR, $\\sp1$H and $\\sp{13}$C NMR spectroscopies, fast-atom bombardment mass spectrometry, and X-ray crystallography.","abstract_html":"The cluster anion ($\\rm Re\\sb7C(CO)\\sb{21}Ir(C\\sb8H\\sb{14})(CO)\\rbrack \\sp{2-}$ has been synthesized by the capping of ($\\rm Re\\sb7C(CO)\\sb{21}\\rbrack \\sp{3-}$ with the in-situ generated cationic species from the reaction of ($\\rm Ir(C\\sb8H\\sb{14})\\sb2(CO)Cl\\rbrack \\sb2$ and AgBF$\\sb4.$ This new heptarhenium-iridium compound reacts with two electron donors to give ligand-substituted compounds ($\\rm Re\\sb7C(CO)\\sb{21}Ir(L)(CO)\\rbrack \\sp{2-}$ (L = CO, $\\rm C\\sb2H\\sb4,$ PMePh$\\sb2,$ and PPh$\\sb3),$ and with triphenylsilane and allyl bromide to form the oxidative addition products ($\\rm Re\\sb7C(CO)\\sb{21}Ir(H)(CO)(SiPh\\sb3)\\rbrack \\sp{2-}$ and ($\\rm Re\\sb7C(CO)\\sb{21}Ir(\\eta\\sp3C\\sb3H\\sb5)(CO)\\rbrack \\sp-.$ The reactivities at iridium parallel those of the indenyl complex $\\rm (\\eta\\sp5C\\sb9H\\sb7)Ir(C\\sb8H\\sb{14})(CO),$ thus giving further support for the previously proposed analogy between ($\\rm Re\\sb7C(CO)\\sb{21}\\rbrack \\sp{3-}$ and the cyclopentadienyl ligand and its derivatives. Formulation and characterization of these new compounds are based on elemental analysis, IR, $\\sp1$H and $\\sp{13}$C NMR spectroscopies, fast-atom bombardment mass spectrometry, and X-ray crystallography.","abstract_has_math":true,"creators":["Ma, Linqing"],"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":"2011-05-07T13:51:40Z","date_published":"2011-05-07T13:51:40Z","updated_at":"2026-07-22T22:25:20Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1991 Ma, Linqing"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210905","(UMI)AAI9210905"],"render_values":[{"text":"AAI9210905","href":null,"code":true},{"text":"(UMI)AAI9210905","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/22793","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":["Ma, Linqing"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:51:40Z","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"]}]},{"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 Ma, Linqing"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210905","(UMI)AAI9210905","http://hdl.handle.net/2142/22793"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The cluster anion ($\\rm Re\\sb7C(CO)\\sb{21}Ir(C\\sb8H\\sb{14})(CO)\\rbrack \\sp{2-}$ has been synthesized by the capping of ($\\rm Re\\sb7C(CO)\\sb{21}\\rbrack \\sp{3-}$ with the in-situ generated cationic species from the reaction of ($\\rm Ir(C\\sb8H\\sb{14})\\sb2(CO)Cl\\rbrack \\sb2$ and AgBF$\\sb4.$ This new heptarhenium-iridium compound reacts with two electron donors to give ligand-substituted compounds ($\\rm Re\\sb7C(CO)\\sb{21}Ir(L)(CO)\\rbrack \\sp{2-}$ (L = CO, $\\rm C\\sb2H\\sb4,$ PMePh$\\sb2,$ and PPh$\\sb3),$ and with triphenylsilane and allyl bromide to form the oxidative addition products ($\\rm Re\\sb7C(CO)\\sb{21}Ir(H)(CO)(SiPh\\sb3)\\rbrack \\sp{2-}$ and ($\\rm Re\\sb7C(CO)\\sb{21}Ir(\\eta\\sp3C\\sb3H\\sb5)(CO)\\rbrack \\sp-.$ The reactivities at iridium parallel those of the indenyl complex $\\rm (\\eta\\sp5C\\sb9H\\sb7)Ir(C\\sb8H\\sb{14})(CO),$ thus giving further support for the previously proposed analogy between ($\\rm Re\\sb7C(CO)\\sb{21}\\rbrack \\sp{3-}$ and the cyclopentadienyl ligand and its derivatives. Formulation and characterization of these new compounds are based on elemental analysis, IR, $\\sp1$H and $\\sp{13}$C NMR spectroscopies, fast-atom bombardment mass spectrometry, and X-ray crystallography.","The cluster anion ($\\rm Re\\sb7C(CO)\\sb{21}Ir(CO)\\sb2\\rbrack \\sp{2-}$ undergoes an irreversible framework isomerization process in solution to form a new isomer $\\rm \\{\\lbrack Re(CO)\\sb3\\rbrack\\sb2\\lbrack Re\\sb5IrC(CO)\\sb{17}\\rbrack \\}\\sp{2-}.$ Kinetic studies have been carried out, and a reaction mechanism has also been proposed. In refluxing acetonitrile $\\rm \\{\\lbrack Re(CO)\\sb3\\rbrack\\sb2\\lbrack Re\\sb5IrC(CO)\\sb{17}\\rbrack \\}\\sp{2-}$ loses a Re(CO)$\\sb3\\sp+$ fragment, leading to the formation of $\\rm \\lbrack Re\\sb6IrC(CO)\\sb{20}\\rbrack \\sp{3-}.$ This analog of $\\rm \\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack \\sp{3-}$ reacts with Au(PPh$\\sb3)$Cl to give ($\\rm Re\\sb6IrC(CO)\\sb{20}Au(PPh\\sb3)\\rbrack \\sp{2-}$ and $\\rm \\{Re\\sb6IrC(CO)\\sb{20}\\lbrack Au(PPh\\sb3)\\rbrack \\sb2\\}\\sp-,$ which have been characterized by $\\sp{31}$P and $\\sp{13}$C NMR studies.","The known cluster anion ($\\rm Ru\\sb{10}C\\sb2(CO)\\sb{24}\\rbrack \\sp{2-}$ can be prepared via an alternative route involving the redox condensation of ($\\rm Ru\\sb6C(CO)\\sb{16}\\rbrack \\sp{2-}$ and Ru$\\sb5$C(CO)$\\sb{15}.$ Substitution of two apical carbonyls in ($\\rm Ru\\sb{10}C\\sb2(CO)\\sb{24}\\rbrack \\sp{2-}$ by one diphenylacetylene molecule gives the compound ($\\rm Ru\\sb{10}C\\sb2(CO)\\sb{22}(C\\sb2Ph\\sb2)\\rbrack \\sp{2-},$ which contains a new ruthenium-ruthenium bond between the two apical atoms in the bioctahedral structure. Carbonyl ligand dynamic exchange behavior has been observed by variable-temperature $\\sp{13}$C NMR spectroscopy.","Made available in DSpace on 2011-05-07T13:51:40Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210905.pdf: 4909884 bytes, checksum: 5aa0c5da05f921f8b07612d18a9a2fb4 (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:00:02Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:28:22-05:00 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 studies of high-nuclearity carbido carbonyl clusters of heptarhenium-iridium and decaruthenium"]}]}],"canonical_facts":{"dc:contributor":["Shapley, John R."],"dc:creator":["Ma, Linqing"],"dc:date":["2011-05-07T13:51:40Z","10000-01-01","1991"],"dc:description":["The cluster anion ($\\rm Re\\sb7C(CO)\\sb{21}Ir(C\\sb8H\\sb{14})(CO)\\rbrack \\sp{2-}$ has been synthesized by the capping of ($\\rm Re\\sb7C(CO)\\sb{21}\\rbrack \\sp{3-}$ with the in-situ generated cationic species from the reaction of ($\\rm Ir(C\\sb8H\\sb{14})\\sb2(CO)Cl\\rbrack \\sb2$ and AgBF$\\sb4.$ This new heptarhenium-iridium compound reacts with two electron donors to give ligand-substituted compounds ($\\rm Re\\sb7C(CO)\\sb{21}Ir(L)(CO)\\rbrack \\sp{2-}$ (L = CO, $\\rm C\\sb2H\\sb4,$ PMePh$\\sb2,$ and PPh$\\sb3),$ and with triphenylsilane and allyl bromide to form the oxidative addition products ($\\rm Re\\sb7C(CO)\\sb{21}Ir(H)(CO)(SiPh\\sb3)\\rbrack \\sp{2-}$ and ($\\rm Re\\sb7C(CO)\\sb{21}Ir(\\eta\\sp3C\\sb3H\\sb5)(CO)\\rbrack \\sp-.$ The reactivities at iridium parallel those of the indenyl complex $\\rm (\\eta\\sp5C\\sb9H\\sb7)Ir(C\\sb8H\\sb{14})(CO),$ thus giving further support for the previously proposed analogy between ($\\rm Re\\sb7C(CO)\\sb{21}\\rbrack \\sp{3-}$ and the cyclopentadienyl ligand and its derivatives. Formulation and characterization of these new compounds are based on elemental analysis, IR, $\\sp1$H and $\\sp{13}$C NMR spectroscopies, fast-atom bombardment mass spectrometry, and X-ray crystallography.","The cluster anion ($\\rm Re\\sb7C(CO)\\sb{21}Ir(CO)\\sb2\\rbrack \\sp{2-}$ undergoes an irreversible framework isomerization process in solution to form a new isomer $\\rm \\{\\lbrack Re(CO)\\sb3\\rbrack\\sb2\\lbrack Re\\sb5IrC(CO)\\sb{17}\\rbrack \\}\\sp{2-}.$ Kinetic studies have been carried out, and a reaction mechanism has also been proposed. In refluxing acetonitrile $\\rm \\{\\lbrack Re(CO)\\sb3\\rbrack\\sb2\\lbrack Re\\sb5IrC(CO)\\sb{17}\\rbrack \\}\\sp{2-}$ loses a Re(CO)$\\sb3\\sp+$ fragment, leading to the formation of $\\rm \\lbrack Re\\sb6IrC(CO)\\sb{20}\\rbrack \\sp{3-}.$ This analog of $\\rm \\lbrack Re\\sb7C(CO)\\sb{21}\\rbrack \\sp{3-}$ reacts with Au(PPh$\\sb3)$Cl to give ($\\rm Re\\sb6IrC(CO)\\sb{20}Au(PPh\\sb3)\\rbrack \\sp{2-}$ and $\\rm \\{Re\\sb6IrC(CO)\\sb{20}\\lbrack Au(PPh\\sb3)\\rbrack \\sb2\\}\\sp-,$ which have been characterized by $\\sp{31}$P and $\\sp{13}$C NMR studies.","The known cluster anion ($\\rm Ru\\sb{10}C\\sb2(CO)\\sb{24}\\rbrack \\sp{2-}$ can be prepared via an alternative route involving the redox condensation of ($\\rm Ru\\sb6C(CO)\\sb{16}\\rbrack \\sp{2-}$ and Ru$\\sb5$C(CO)$\\sb{15}.$ Substitution of two apical carbonyls in ($\\rm Ru\\sb{10}C\\sb2(CO)\\sb{24}\\rbrack \\sp{2-}$ by one diphenylacetylene molecule gives the compound ($\\rm Ru\\sb{10}C\\sb2(CO)\\sb{22}(C\\sb2Ph\\sb2)\\rbrack \\sp{2-},$ which contains a new ruthenium-ruthenium bond between the two apical atoms in the bioctahedral structure. Carbonyl ligand dynamic exchange behavior has been observed by variable-temperature $\\sp{13}$C NMR spectroscopy.","Made available in DSpace on 2011-05-07T13:51:40Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210905.pdf: 4909884 bytes, checksum: 5aa0c5da05f921f8b07612d18a9a2fb4 (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:00:02Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:28:22-05:00 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":["AAI9210905","(UMI)AAI9210905","http://hdl.handle.net/2142/22793"],"dc:language":["eng"],"dc:rights":["Copyright 1991 Ma, Linqing"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Synthesis and reactivity studies of high-nuclearity carbido carbonyl clusters of heptarhenium-iridium and decaruthenium"],"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"}