{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/20150"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/20150","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis and properties of mononuclear and polynuclear indenyl iridium complexes","abstract":"The reaction of $\\rm Ir(CO)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm Ir(\\eta\\sp2$-$\\rm C\\sb2H\\sb4)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ provided $\\rm Ir\\sb3(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$, and the reaction of $\\rm Ir(CO)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm Rh(\\eta\\sp2$-$\\rm C\\sb2H\\sb4)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ provided $\\rm Ir\\sb{3-x}Rh\\sb{x}(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ (x = 0 - 3) in good yields. These compounds react readily with carbon monoxide or PPh$\\sb3$ at room temperature to form mononuclear products.","abstract_html":"The reaction of $\\rm Ir(CO)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm Ir(\\eta\\sp2$-$\\rm C\\sb2H\\sb4)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ provided <span class=\"etd-inline-math\">\\rm Ir\\sb3(&mu;</span>-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$, and the reaction of $\\rm Ir(CO)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm Rh(\\eta\\sp2$-$\\rm C\\sb2H\\sb4)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ provided <span class=\"etd-inline-math\">\\rm Ir\\sb{3-x}Rh\\sb{x}(&mu;</span>-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ (x = 0 - 3) in good yields. These compounds react readily with carbon monoxide or PPh$\\sb3$ at room temperature to form mononuclear products.","abstract_has_math":true,"creators":["Comstock, Matthew Christian"],"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":"2011-05-07T12:30:24Z","date_published":"2011-05-07T12:30:24Z","updated_at":"2026-07-22T22:25:15Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1996 Comstock, Matthew Christian"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591197792","AAI9712238","(UMI)AAI9712238"],"render_values":[{"text":"9780591197792","href":null,"code":true},{"text":"AAI9712238","href":null,"code":true},{"text":"(UMI)AAI9712238","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/20150","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":["Comstock, Matthew Christian"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:30:24Z","10000-01-01","1996"]},{"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 1996 Comstock, Matthew Christian"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591197792","AAI9712238","(UMI)AAI9712238","http://hdl.handle.net/2142/20150"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The reaction of $\\rm Ir(CO)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm Ir(\\eta\\sp2$-$\\rm C\\sb2H\\sb4)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ provided $\\rm Ir\\sb3(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$, and the reaction of $\\rm Ir(CO)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm Rh(\\eta\\sp2$-$\\rm C\\sb2H\\sb4)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ provided $\\rm Ir\\sb{3-x}Rh\\sb{x}(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ (x = 0 - 3) in good yields. These compounds react readily with carbon monoxide or PPh$\\sb3$ at room temperature to form mononuclear products.","The reaction of $\\rm Ir\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ with HBF$\\rm\\sb4\\cdot Et\\sb2$O gave $\\rm\\lbrack Ir\\sb3(\\mu$-$\\rm H)(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3\\rbrack\\lbrack BF\\sb4$). Subsequent deprotonation led to generation of $\\rm C\\sb{S}$-$\\rm Ir\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$, which rapidly reverted to an equilibrium mixture containing major isomer $\\rm C\\sb{3v}$-$\\rm Ir\\sb3(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ and minor isomer $\\rm C\\sb{S}$-$\\rm Ir\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$. Variable temperature NMR experiments indicated that $\\rm C\\sb{S}$-$\\rm Ir\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ undergoes a dynamic process that involves a third isomer of $\\rm Ir\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$. This study provides a unique set of relative energies in solution for three of the four observed forms for a $\\rm M\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm L)\\sb3$ system.","The reactions of $\\rm C\\sb{3v}$-$\\rm Ir\\sb3(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ with metal fragment electrophiles containing Cu, Ag, Au, or Hg provided cationic tetranuclear clusters, which show a rearrangement of the $\\rm Ir\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ moiety to a $\\rm C\\sb{S}$ geometry. The reaction with TIPF$\\sb6$ gave $\\rm\\lbrack Ir\\sb3Tl(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3\\rbrack\\lbrack PF\\sb6$), which maintains $\\rm C\\sb{3v}$ geometry and has the thallium ion encapsulated by the six-membered rings of the indenyl ligands.","The reaction of $\\rm Ir(CO)(\\eta\\sp2$-$\\rm C\\sb8H\\sb{14})(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm Re\\sb2(\\mu$-$\\rm H)\\sb2(CO)\\sb8$ formed the mixed-metal cluster $\\rm IrRe\\sb2(\\mu$-$\\rm H)\\sb2(CO)\\sb9(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$. Deprotonation with KOH/EtOH and addition of (PPN) (Cl) provided $\\rm\\lbrack PPN\\rbrack\\lbrack IrRe\\sb2(\\mu$-$\\rm H)(CO)\\sb9(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$). Addition of PPh$\\sb3$ to $\\rm IrRe\\sb2(\\mu$-$\\rm H)\\sb2(CO)\\sb9(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ led to the carbonyl substitution product $\\rm IrRe\\sb2(\\mu$-$\\rm H)\\sb2(CO)\\sb8(PPh\\sb3)(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$, which contains the phosphine ligand on a rhenium atom, as well as to cluster fragmentation.","The reactions of $\\rm Ir(CO)(\\eta\\sp2$-$\\rm C\\sb8H\\sb{14})(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm C\\sb2R\\sb2$ led to $\\rm Ir(CO)(\\eta\\sp2$-$\\rm C\\sb2R\\sb2)(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ and $\\rm Ir\\sb2(CO)\\sb2(\\mu$-$\\rm C\\sb2R\\sb2)(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb2$ (R = Ph, Tol). Also, alkyne coupling and activation of a C-H bond in the arene solvent formed a novel mononuclear compound containing a substituted butadiene ligand.","Made available in DSpace on 2011-05-07T12:30:24Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712238.pdf: 5994804 bytes, checksum: c9b52ac7f8282a3f1f65f3451a2bc2c4 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:41:54Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:11-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Synthesis and properties of mononuclear and polynuclear indenyl iridium complexes"]}]}],"canonical_facts":{"dc:contributor":["Shapley, John R."],"dc:creator":["Comstock, Matthew Christian"],"dc:date":["2011-05-07T12:30:24Z","10000-01-01","1996"],"dc:description":["The reaction of $\\rm Ir(CO)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm Ir(\\eta\\sp2$-$\\rm C\\sb2H\\sb4)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ provided $\\rm Ir\\sb3(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$, and the reaction of $\\rm Ir(CO)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm Rh(\\eta\\sp2$-$\\rm C\\sb2H\\sb4)\\sb2(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ provided $\\rm Ir\\sb{3-x}Rh\\sb{x}(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ (x = 0 - 3) in good yields. These compounds react readily with carbon monoxide or PPh$\\sb3$ at room temperature to form mononuclear products.","The reaction of $\\rm Ir\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ with HBF$\\rm\\sb4\\cdot Et\\sb2$O gave $\\rm\\lbrack Ir\\sb3(\\mu$-$\\rm H)(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3\\rbrack\\lbrack BF\\sb4$). Subsequent deprotonation led to generation of $\\rm C\\sb{S}$-$\\rm Ir\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$, which rapidly reverted to an equilibrium mixture containing major isomer $\\rm C\\sb{3v}$-$\\rm Ir\\sb3(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ and minor isomer $\\rm C\\sb{S}$-$\\rm Ir\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$. Variable temperature NMR experiments indicated that $\\rm C\\sb{S}$-$\\rm Ir\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ undergoes a dynamic process that involves a third isomer of $\\rm Ir\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$. This study provides a unique set of relative energies in solution for three of the four observed forms for a $\\rm M\\sb3(CO)\\sb3(\\eta\\sp5$-$\\rm L)\\sb3$ system.","The reactions of $\\rm C\\sb{3v}$-$\\rm Ir\\sb3(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ with metal fragment electrophiles containing Cu, Ag, Au, or Hg provided cationic tetranuclear clusters, which show a rearrangement of the $\\rm Ir\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3$ moiety to a $\\rm C\\sb{S}$ geometry. The reaction with TIPF$\\sb6$ gave $\\rm\\lbrack Ir\\sb3Tl(\\mu$-$\\rm CO)\\sb3(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb3\\rbrack\\lbrack PF\\sb6$), which maintains $\\rm C\\sb{3v}$ geometry and has the thallium ion encapsulated by the six-membered rings of the indenyl ligands.","The reaction of $\\rm Ir(CO)(\\eta\\sp2$-$\\rm C\\sb8H\\sb{14})(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm Re\\sb2(\\mu$-$\\rm H)\\sb2(CO)\\sb8$ formed the mixed-metal cluster $\\rm IrRe\\sb2(\\mu$-$\\rm H)\\sb2(CO)\\sb9(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$. Deprotonation with KOH/EtOH and addition of (PPN) (Cl) provided $\\rm\\lbrack PPN\\rbrack\\lbrack IrRe\\sb2(\\mu$-$\\rm H)(CO)\\sb9(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$). Addition of PPh$\\sb3$ to $\\rm IrRe\\sb2(\\mu$-$\\rm H)\\sb2(CO)\\sb9(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ led to the carbonyl substitution product $\\rm IrRe\\sb2(\\mu$-$\\rm H)\\sb2(CO)\\sb8(PPh\\sb3)(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$, which contains the phosphine ligand on a rhenium atom, as well as to cluster fragmentation.","The reactions of $\\rm Ir(CO)(\\eta\\sp2$-$\\rm C\\sb8H\\sb{14})(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ with $\\rm C\\sb2R\\sb2$ led to $\\rm Ir(CO)(\\eta\\sp2$-$\\rm C\\sb2R\\sb2)(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)$ and $\\rm Ir\\sb2(CO)\\sb2(\\mu$-$\\rm C\\sb2R\\sb2)(\\eta\\sp5$-$\\rm C\\sb9H\\sb7)\\sb2$ (R = Ph, Tol). Also, alkyne coupling and activation of a C-H bond in the arene solvent formed a novel mononuclear compound containing a substituted butadiene ligand.","Made available in DSpace on 2011-05-07T12:30:24Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712238.pdf: 5994804 bytes, checksum: c9b52ac7f8282a3f1f65f3451a2bc2c4 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:41:54Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:11-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["9780591197792","AAI9712238","(UMI)AAI9712238","http://hdl.handle.net/2142/20150"],"dc:language":["eng"],"dc:rights":["Copyright 1996 Comstock, Matthew Christian"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Synthesis and properties of mononuclear and polynuclear indenyl iridium 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"}