{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70374"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70374","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis and Structure of Polyoxoanion Supported Organorhodium (I) and Organoiridium (I) Complexes","abstract":"The iridium 1,5-cyclooctadiene Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ adduct $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack\\sb5(Nb\\sb2W\\sb4O\\sb )}\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ (1) has been prepared by reaction of 2.5 eg of $\\lbrack{\\rm Ir(C\\sb8H\\sb )(NCCH\\sb3)\\sb2\\rbrack PF\\sb6}$ with (Nb$\\sb2$W$\\sb4$O$\\sb )\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb4.$ NMR and IR data suggests the anion of 1 is isostructural with the anion of $\\{\\lbrack({\\rm C\\sb7H\\sb8)Rh\\rbrack\\sb{5}(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ (2) reported previously. In 1, two Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ anions act as pentadentate bridging ligands in which both terminal and bridging oxygens are utilized to bind five (C$\\sb8$H$\\sb $)Ir$\\sp+$ units. Reaction of compound 1 with 3 eq of (Nb$\\sb2$W$\\sb4$O$\\sb )\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb4$ in acetonitrile followed by addition of 1 eq of acetic acid results in the formation of $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack\\sb2H(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb5$ (3). In the anion of 3, one two-coordinate proton and two four-coordinate (C$\\sb8$H$\\sb $)Ir$\\sp+$ units link together the two Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ anions. The ONb$\\sb2$ and ONb oxygens are utilized in binding to the proton and (C$\\sb8$H$\\sb $)Ir$\\sp+$ units respectively. Reaction of $\\lbrack{\\rm Ir(C\\sb8H\\sb )(NCCH\\sb3)\\sb2\\rbrack PF}\\sb6$ with (P$\\sb3$O$\\sb9)\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ in methylene chloride has resulted in isolation of $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack(P\\sb3O\\sb9})\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (4a). The P$\\sb3$O$\\sb9\\sp{3-}$ anion is bound to iridium in a tridentate fashion making the coordination geometry around Ir$\\sp{\\rm I}$ approximately square pyramidal.","abstract_html":"The iridium 1,5-cyclooctadiene Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ adduct $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack\\sb5(Nb\\sb2W\\sb4O\\sb )}\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ (1) has been prepared by reaction of 2.5 eg of $\\lbrack{\\rm Ir(C\\sb8H\\sb )(NCCH\\sb3)\\sb2\\rbrack PF\\sb6}$ with (Nb$\\sb2$W$\\sb4$O$\\sb )\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb4.$ NMR and IR data suggests the anion of 1 is isostructural with the anion of $\\{\\lbrack({\\rm C\\sb7H\\sb8)Rh\\rbrack\\sb{5}(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ (2) reported previously. In 1, two Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ anions act as pentadentate bridging ligands in which both terminal and bridging oxygens are utilized to bind five (C$\\sb8$H$\\sb $)Ir$\\sp+$ units. Reaction of compound 1 with 3 eq of (Nb$\\sb2$W$\\sb4$O$\\sb )\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb4$ in acetonitrile followed by addition of 1 eq of acetic acid results in the formation of $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack\\sb2H(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb5$ (3). In the anion of 3, one two-coordinate proton and two four-coordinate (C$\\sb8$H$\\sb $)Ir$\\sp+$ units link together the two Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ anions. The ONb$\\sb2$ and ONb oxygens are utilized in binding to the proton and (C$\\sb8$H$\\sb $)Ir$\\sp+$ units respectively. Reaction of $\\lbrack{\\rm Ir(C\\sb8H\\sb )(NCCH\\sb3)\\sb2\\rbrack PF}\\sb6$ with (P$\\sb3$O$\\sb9)\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ in methylene chloride has resulted in isolation of $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack(P\\sb3O\\sb9})\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (4a). The P$\\sb3$O$\\sb9\\sp{3-}$ anion is bound to iridium in a tridentate fashion making the coordination geometry around Ir$\\sp{\\rm I}$ approximately square pyramidal.","abstract_has_math":true,"creators":["Main, Deborah Jean"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:19:00Z","date_published":"2014-12-15T23:19:00Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8721702"],"render_values":[{"text":"(UMI)AAI8721702","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70374","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Main, Deborah Jean"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:19:00Z","10000-01-01","1987"]},{"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":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/70374","(UMI)AAI8721702"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The iridium 1,5-cyclooctadiene Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ adduct $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack\\sb5(Nb\\sb2W\\sb4O\\sb )}\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ (1) has been prepared by reaction of 2.5 eg of $\\lbrack{\\rm Ir(C\\sb8H\\sb )(NCCH\\sb3)\\sb2\\rbrack PF\\sb6}$ with (Nb$\\sb2$W$\\sb4$O$\\sb )\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb4.$ NMR and IR data suggests the anion of 1 is isostructural with the anion of $\\{\\lbrack({\\rm C\\sb7H\\sb8)Rh\\rbrack\\sb{5}(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ (2) reported previously. In 1, two Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ anions act as pentadentate bridging ligands in which both terminal and bridging oxygens are utilized to bind five (C$\\sb8$H$\\sb $)Ir$\\sp+$ units. Reaction of compound 1 with 3 eq of (Nb$\\sb2$W$\\sb4$O$\\sb )\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb4$ in acetonitrile followed by addition of 1 eq of acetic acid results in the formation of $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack\\sb2H(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb5$ (3). In the anion of 3, one two-coordinate proton and two four-coordinate (C$\\sb8$H$\\sb $)Ir$\\sp+$ units link together the two Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ anions. The ONb$\\sb2$ and ONb oxygens are utilized in binding to the proton and (C$\\sb8$H$\\sb $)Ir$\\sp+$ units respectively. Reaction of $\\lbrack{\\rm Ir(C\\sb8H\\sb )(NCCH\\sb3)\\sb2\\rbrack PF}\\sb6$ with (P$\\sb3$O$\\sb9)\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ in methylene chloride has resulted in isolation of $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack(P\\sb3O\\sb9})\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (4a). The P$\\sb3$O$\\sb9\\sp{3-}$ anion is bound to iridium in a tridentate fashion making the coordination geometry around Ir$\\sp{\\rm I}$ approximately square pyramidal.","The metal dicarbonyl polyoxoanion adducts $\\{\\lbrack({\\rm CO)\\sb2Rh\\rbrack\\sb5(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ (8), $\\{\\lbrack({\\rm CO)\\sb2Rh\\rbrack\\sb3(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb5$ (9), $\\{\\lbrack({\\rm CO)\\sb2Ir\\rbrack\\sb2H(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb5$ (10), and $\\{\\lbrack({\\rm CO)\\sb2Ir\\rbrack(P\\sb3O\\sb9)\\}\\lbrack(C\\sb6H\\sb5)\\sb3PNP(C\\sb6H}\\sb5)\\sb3\\rbrack\\sb2$ (11) have been prepared and characterized. Compounds 8, 10, and 11 are synthesized by carbonylation of their respective diene analogs, whereas compound 9 is prepared from (Rh(CO)$\\sb2$Cl) $\\sb2$ and (Nb$\\sb2$W$\\sb4$O$\\sb )\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb4.$ Based on IR and NMR data, compounds 8, 10, and 11 exhibit the same anion structures as their respective diene analogs.","The novel reaction of $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack(P\\sb3O\\sb9})\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (4a) with dioxygen is reported. In 1,2-dichloroethane at 55-60$\\sp\\circ$, dioxygen reacts with 4a to form $\\{\\lbrack(\\eta\\sp1,\\eta\\sp3{\\rm C\\sb8H\\sb OH)Ir\\rbrack(P\\sb3O\\sb9})\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (13). A single crystal X-ray diffraction study of 13 shows the Ir$\\sp{\\rm III}$ atom to be bonded to three oxygens of the P$\\sb3$O$\\sb9\\sp{3-}$ ligand and to four carbons of the C$\\sb8$H$\\sb $OH ring, making the coordination geometry around iridium octahedral if the allyl function is regarded as occupying two coordination sites. (Abstract shortened with permission of author.)","Made available in DSpace on 2014-12-15T23:19:00Z (GMT). No. of bitstreams: 1 8721702.pdf: 3538096 bytes, checksum: dc73e9da86dc46ae7c6059352f6222bf (MD5) Previous issue date: 1987","Embargo set by: Seth Robbins for item 70540 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","126 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987."]},{"key":"dc:title","label":"Title","values":["Synthesis and Structure of Polyoxoanion Supported Organorhodium (I) and Organoiridium (I) Complexes"]}]}],"canonical_facts":{"dc:creator":["Main, Deborah Jean"],"dc:date":["2014-12-15T23:19:00Z","10000-01-01","1987"],"dc:description":["The iridium 1,5-cyclooctadiene Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ adduct $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack\\sb5(Nb\\sb2W\\sb4O\\sb )}\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ (1) has been prepared by reaction of 2.5 eg of $\\lbrack{\\rm Ir(C\\sb8H\\sb )(NCCH\\sb3)\\sb2\\rbrack PF\\sb6}$ with (Nb$\\sb2$W$\\sb4$O$\\sb )\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb4.$ NMR and IR data suggests the anion of 1 is isostructural with the anion of $\\{\\lbrack({\\rm C\\sb7H\\sb8)Rh\\rbrack\\sb{5}(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ (2) reported previously. In 1, two Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ anions act as pentadentate bridging ligands in which both terminal and bridging oxygens are utilized to bind five (C$\\sb8$H$\\sb $)Ir$\\sp+$ units. Reaction of compound 1 with 3 eq of (Nb$\\sb2$W$\\sb4$O$\\sb )\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb4$ in acetonitrile followed by addition of 1 eq of acetic acid results in the formation of $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack\\sb2H(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb5$ (3). In the anion of 3, one two-coordinate proton and two four-coordinate (C$\\sb8$H$\\sb $)Ir$\\sp+$ units link together the two Nb$\\sb2$W$\\sb4$O$\\sb \\sp{4-}$ anions. The ONb$\\sb2$ and ONb oxygens are utilized in binding to the proton and (C$\\sb8$H$\\sb $)Ir$\\sp+$ units respectively. Reaction of $\\lbrack{\\rm Ir(C\\sb8H\\sb )(NCCH\\sb3)\\sb2\\rbrack PF}\\sb6$ with (P$\\sb3$O$\\sb9)\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ in methylene chloride has resulted in isolation of $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack(P\\sb3O\\sb9})\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (4a). The P$\\sb3$O$\\sb9\\sp{3-}$ anion is bound to iridium in a tridentate fashion making the coordination geometry around Ir$\\sp{\\rm I}$ approximately square pyramidal.","The metal dicarbonyl polyoxoanion adducts $\\{\\lbrack({\\rm CO)\\sb2Rh\\rbrack\\sb5(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb3$ (8), $\\{\\lbrack({\\rm CO)\\sb2Rh\\rbrack\\sb3(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb5$ (9), $\\{\\lbrack({\\rm CO)\\sb2Ir\\rbrack\\sb2H(Nb\\sb2W\\sb4O\\sb })\\sb2\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb5$ (10), and $\\{\\lbrack({\\rm CO)\\sb2Ir\\rbrack(P\\sb3O\\sb9)\\}\\lbrack(C\\sb6H\\sb5)\\sb3PNP(C\\sb6H}\\sb5)\\sb3\\rbrack\\sb2$ (11) have been prepared and characterized. Compounds 8, 10, and 11 are synthesized by carbonylation of their respective diene analogs, whereas compound 9 is prepared from (Rh(CO)$\\sb2$Cl) $\\sb2$ and (Nb$\\sb2$W$\\sb4$O$\\sb )\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb4.$ Based on IR and NMR data, compounds 8, 10, and 11 exhibit the same anion structures as their respective diene analogs.","The novel reaction of $\\{\\lbrack({\\rm C\\sb8H\\sb )Ir\\rbrack(P\\sb3O\\sb9})\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (4a) with dioxygen is reported. In 1,2-dichloroethane at 55-60$\\sp\\circ$, dioxygen reacts with 4a to form $\\{\\lbrack(\\eta\\sp1,\\eta\\sp3{\\rm C\\sb8H\\sb OH)Ir\\rbrack(P\\sb3O\\sb9})\\}\\lbrack(n$-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ (13). A single crystal X-ray diffraction study of 13 shows the Ir$\\sp{\\rm III}$ atom to be bonded to three oxygens of the P$\\sb3$O$\\sb9\\sp{3-}$ ligand and to four carbons of the C$\\sb8$H$\\sb $OH ring, making the coordination geometry around iridium octahedral if the allyl function is regarded as occupying two coordination sites. (Abstract shortened with permission of author.)","Made available in DSpace on 2014-12-15T23:19:00Z (GMT). No. of bitstreams: 1 8721702.pdf: 3538096 bytes, checksum: dc73e9da86dc46ae7c6059352f6222bf (MD5) Previous issue date: 1987","Embargo set by: Seth Robbins for item 70540 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","126 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987."],"dc:identifier":["http://hdl.handle.net/2142/70374","(UMI)AAI8721702"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Synthesis and Structure of Polyoxoanion Supported Organorhodium (I) and Organoiridium (I) 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":"2026-07-22T22:26:02Z"}