{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/20337"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/20337","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Substitution and redox reactions of heptarhenium cluster derivatives","abstract":"The second-order rate constants for the reactivity of (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ towards phosphorus donors were determined. In order to correlate the results to electronic and/or steric effects, steric profiles relating log k$\\sb2$ to an intrinsic reactivity $(\\alpha),$ an electronic parameter $(\\beta),$ and a steric parameter $(\\theta)$ were constructed. From differences in intrinsic reactivity for phosphines and phosphites, an intermediate configuration involving a bridging carbonyl has been proposed for the reaction of (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ with various phosphorus donors (PY$\\sb3).$","abstract_html":"The second-order rate constants for the reactivity of (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ towards phosphorus donors were determined. In order to correlate the results to electronic and/or steric effects, steric profiles relating log k$\\sb2$ to an intrinsic reactivity <span class=\"etd-inline-math\">(&alpha;),</span> an electronic parameter <span class=\"etd-inline-math\">(&beta;),</span> and a steric parameter <span class=\"etd-inline-math\">(&theta;)</span> were constructed. From differences in intrinsic reactivity for phosphines and phosphites, an intermediate configuration involving a bridging carbonyl has been proposed for the reaction of (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ with various phosphorus donors (PY$\\sb3).$","abstract_has_math":true,"creators":["Simerly, Scott W."],"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":"2011-05-07T12:36:21Z","date_published":"2011-05-07T12:36:21Z","updated_at":"2026-07-22T22:25:15Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1991 Simerly, Scott W."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210992","(UMI)AAI9210992"],"render_values":[{"text":"AAI9210992","href":null,"code":true},{"text":"(UMI)AAI9210992","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/20337","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":["Simerly, Scott W."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:36:21Z","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 Simerly, Scott W."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210992","(UMI)AAI9210992","http://hdl.handle.net/2142/20337"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The second-order rate constants for the reactivity of (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ towards phosphorus donors were determined. In order to correlate the results to electronic and/or steric effects, steric profiles relating log k$\\sb2$ to an intrinsic reactivity $(\\alpha),$ an electronic parameter $(\\beta),$ and a steric parameter $(\\theta)$ were constructed. From differences in intrinsic reactivity for phosphines and phosphites, an intermediate configuration involving a bridging carbonyl has been proposed for the reaction of (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ with various phosphorus donors (PY$\\sb3).$","Nitrosylation of a series of mixed-metal heptarhenium clusters, (Re$\\sb7$C(CO)$\\sb{21}$ML$\\sb{\\rm n}$) $\\sp{2-},$ gave the mono-substituted products, (Re$\\sb7$C(CO)$\\sb{20}$ML$\\sb{\\rm n}\\rbrack\\sp-.$ A variety of spectroscopic techniques were used to characterize the reaction products. Variable temperature $\\sp{13}$C NMR studies determined the solution structure of (Re$\\sb7$C(CO)$\\sb{20}$(NO)Rh(CO)$\\sb2$) $\\sp-.$ From kinetic studies, the nitrosyl substituted cluster (Re$\\sb7$C(CO)$\\sb{20}$(NO)Rh(CO)$\\sb2$) $\\sp-$ exhibits enhanced reactivity toward phosphorus ligands in comparison with (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}.$","The carbonyl ligands bound to (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ display unusual intermolecular and intramolecular exchange. Upon treatment with $\\sp{13}$CO, (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ is selectively $\\sp{13}$CO enriched to ($\\rm Re(CO)\\sb3Re\\sb6C(\\sp{13}CO)\\sb{18}Rh(\\sp{13}CO)\\sb2\\rbrack \\sp{2-}$. A capping Re(CO)$\\sb3$ moiety trans to the rhodium cap remains unenriched. Formation of the radical species (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2\\rbrack\\sp-$ by chemical oxidation results in complete carbonyl scrambling, which is revealed upon reduction to the parent cluster ($\\rm Re(\\sp{13}CO)\\sb3Re\\sb6C(\\sp{13}CO)\\sb{18}Rh(\\sp{13}CO)\\sb 2\\rbrack \\sp{2-}.$ The selectively $\\sp{13}$Co enriched cluster (Re(CO)$\\sb3$Re$\\sb6$C($\\sp{13}$CO)$\\sb{18}$) $\\sp{2-}$ has been formed in a decapping reaction of ($\\rm Re(CO)\\sb3Re\\sb6C(\\sp{13}CO)\\sb{18}Rh(\\sp{13}CO\\sb2\\rbrack \\sp{2-}$ with excess PPh$\\sb3$ in acetonitrile.","Two-electron oxidation of (Re$\\sb7$C(CO)$\\sb{21}$) $\\sp{3-}$ in the presence of P(OPh)$\\sb3$ affords (Re$\\sb7$C(CO)$\\sb{21}$(P(OPh)$\\sb3)$) $\\sp-.$ $\\sp{13}$C NMR indicates that this cluster exhibits partial charge separation. (Re$\\sb7$C(CO)$\\sb{21}$(P(OPh)$\\sb3)$) $\\sp-$ decomposes in acetonitrile to form (Re$\\sb6$C(CO)$\\sb{19}$) $\\sp{2-}$ and (Re(CO)$\\sb3$(P(OPh)$\\sb3)\\sb2$(NCCH$\\sb3)$) $\\sp+,$ and therefore it represents a directly observed intermediate in a cluster decapping reaction.","Made available in DSpace on 2011-05-07T12:36:21Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210992.pdf: 3597419 bytes, checksum: beff29c7e5a9997a87eabf013f1fad00 (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:43:13Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:53-05:00 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":["Substitution and redox reactions of heptarhenium cluster derivatives"]}]}],"canonical_facts":{"dc:contributor":["Shapley, John R."],"dc:creator":["Simerly, Scott W."],"dc:date":["2011-05-07T12:36:21Z","10000-01-01","1991"],"dc:description":["The second-order rate constants for the reactivity of (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ towards phosphorus donors were determined. In order to correlate the results to electronic and/or steric effects, steric profiles relating log k$\\sb2$ to an intrinsic reactivity $(\\alpha),$ an electronic parameter $(\\beta),$ and a steric parameter $(\\theta)$ were constructed. From differences in intrinsic reactivity for phosphines and phosphites, an intermediate configuration involving a bridging carbonyl has been proposed for the reaction of (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ with various phosphorus donors (PY$\\sb3).$","Nitrosylation of a series of mixed-metal heptarhenium clusters, (Re$\\sb7$C(CO)$\\sb{21}$ML$\\sb{\\rm n}$) $\\sp{2-},$ gave the mono-substituted products, (Re$\\sb7$C(CO)$\\sb{20}$ML$\\sb{\\rm n}\\rbrack\\sp-.$ A variety of spectroscopic techniques were used to characterize the reaction products. Variable temperature $\\sp{13}$C NMR studies determined the solution structure of (Re$\\sb7$C(CO)$\\sb{20}$(NO)Rh(CO)$\\sb2$) $\\sp-.$ From kinetic studies, the nitrosyl substituted cluster (Re$\\sb7$C(CO)$\\sb{20}$(NO)Rh(CO)$\\sb2$) $\\sp-$ exhibits enhanced reactivity toward phosphorus ligands in comparison with (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}.$","The carbonyl ligands bound to (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ display unusual intermolecular and intramolecular exchange. Upon treatment with $\\sp{13}$CO, (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2$) $\\sp{2-}$ is selectively $\\sp{13}$CO enriched to ($\\rm Re(CO)\\sb3Re\\sb6C(\\sp{13}CO)\\sb{18}Rh(\\sp{13}CO)\\sb2\\rbrack \\sp{2-}$. A capping Re(CO)$\\sb3$ moiety trans to the rhodium cap remains unenriched. Formation of the radical species (Re$\\sb7$C(CO)$\\sb{21}$Rh(CO)$\\sb2\\rbrack\\sp-$ by chemical oxidation results in complete carbonyl scrambling, which is revealed upon reduction to the parent cluster ($\\rm Re(\\sp{13}CO)\\sb3Re\\sb6C(\\sp{13}CO)\\sb{18}Rh(\\sp{13}CO)\\sb 2\\rbrack \\sp{2-}.$ The selectively $\\sp{13}$Co enriched cluster (Re(CO)$\\sb3$Re$\\sb6$C($\\sp{13}$CO)$\\sb{18}$) $\\sp{2-}$ has been formed in a decapping reaction of ($\\rm Re(CO)\\sb3Re\\sb6C(\\sp{13}CO)\\sb{18}Rh(\\sp{13}CO\\sb2\\rbrack \\sp{2-}$ with excess PPh$\\sb3$ in acetonitrile.","Two-electron oxidation of (Re$\\sb7$C(CO)$\\sb{21}$) $\\sp{3-}$ in the presence of P(OPh)$\\sb3$ affords (Re$\\sb7$C(CO)$\\sb{21}$(P(OPh)$\\sb3)$) $\\sp-.$ $\\sp{13}$C NMR indicates that this cluster exhibits partial charge separation. (Re$\\sb7$C(CO)$\\sb{21}$(P(OPh)$\\sb3)$) $\\sp-$ decomposes in acetonitrile to form (Re$\\sb6$C(CO)$\\sb{19}$) $\\sp{2-}$ and (Re(CO)$\\sb3$(P(OPh)$\\sb3)\\sb2$(NCCH$\\sb3)$) $\\sp+,$ and therefore it represents a directly observed intermediate in a cluster decapping reaction.","Made available in DSpace on 2011-05-07T12:36:21Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210992.pdf: 3597419 bytes, checksum: beff29c7e5a9997a87eabf013f1fad00 (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:43:13Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:53-05:00 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":["AAI9210992","(UMI)AAI9210992","http://hdl.handle.net/2142/20337"],"dc:language":["eng"],"dc:rights":["Copyright 1991 Simerly, Scott W."],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Substitution and redox reactions of heptarhenium cluster derivatives"],"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"}