{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70399"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70399","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis, Structure, and Reactivity of High-Nuclearity Carbido Clusters of Rhenium","abstract":"The cluster anion (Re$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{3-}$ reacts with late transition metal-based electrophiles to yield the mixed-metal clusters (Re$\\sb7$C(CO)$\\sb{21}$ML$\\sb{\\rm n}\\rbrack\\sp{2-}$ and with H$\\sp+$ to yield the hydrido species (HRe$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{2-}$. These complexes have been fully characterized by IR, $\\sp1$H NMR, and fast-atom bombardment mass spectroscopies. $\\sp1$H and $\\sp $C NMR, IR, and cyclic voltammetry studies on selected complexes indicate that the (Re$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{3-}$ cap is a poorer electron donor to the ML$\\sb{\\rm n}\\sp+$ moiety than the cyclopentadienide ligand in the analogous compounds $(\\eta\\sp5$-C$\\sb5$H$\\sb5$)ML$\\sb{\\rm n}$. Variable-temperature $\\sp $C NMR studies and X-ray diffraction experiments on several of the mixed-metal clusters demonstrate that each of these compounds adopts a trans-bicapped octahedral configuration of metal atoms, i.e., the ML$\\sb{\\rm n}$ fragment symmetrically caps the triangular face opposite the unique Re(CO)$\\sb3$ group. The compound (HRe$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{2-}$ is a mixture of two isomers, which differ in the position of the hydride ligand on the metal framework.","abstract_html":"The cluster anion (Re$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{3-}$ reacts with late transition metal-based electrophiles to yield the mixed-metal clusters (Re$\\sb7$C(CO)$\\sb{21}$ML$\\sb{\\rm n}\\rbrack\\sp{2-}$ and with H$\\sp+$ to yield the hydrido species (HRe$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{2-}$. These complexes have been fully characterized by IR, $\\sp1$H NMR, and fast-atom bombardment mass spectroscopies. $\\sp1$H and $\\sp $C NMR, IR, and cyclic voltammetry studies on selected complexes indicate that the (Re$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{3-}$ cap is a poorer electron donor to the ML$\\sb{\\rm n}\\sp+$ moiety than the cyclopentadienide ligand in the analogous compounds $(\\eta\\sp5$-C$\\sb5$H$\\sb5$)ML$\\sb{\\rm n}$. Variable-temperature $\\sp $C NMR studies and X-ray diffraction experiments on several of the mixed-metal clusters demonstrate that each of these compounds adopts a trans-bicapped octahedral configuration of metal atoms, i.e., the ML$\\sb{\\rm n}$ fragment symmetrically caps the triangular face opposite the unique Re(CO)$\\sb3$ group. The compound (HRe$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{2-}$ is a mixture of two isomers, which differ in the position of the hydride ligand on the metal framework.","abstract_has_math":true,"creators":["Henly, Timothy James"],"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":2014,"date_issued":"2014-12-15T23:19:10Z","date_published":"2014-12-15T23:19:10Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8815352"],"render_values":[{"text":"(UMI)AAI8815352","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70399","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":["Henly, Timothy James"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:19:10Z","10000-01-01","1988"]},{"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/2142/70399","(UMI)AAI8815352"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The cluster anion (Re$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{3-}$ reacts with late transition metal-based electrophiles to yield the mixed-metal clusters (Re$\\sb7$C(CO)$\\sb{21}$ML$\\sb{\\rm n}\\rbrack\\sp{2-}$ and with H$\\sp+$ to yield the hydrido species (HRe$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{2-}$. These complexes have been fully characterized by IR, $\\sp1$H NMR, and fast-atom bombardment mass spectroscopies. $\\sp1$H and $\\sp $C NMR, IR, and cyclic voltammetry studies on selected complexes indicate that the (Re$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{3-}$ cap is a poorer electron donor to the ML$\\sb{\\rm n}\\sp+$ moiety than the cyclopentadienide ligand in the analogous compounds $(\\eta\\sp5$-C$\\sb5$H$\\sb5$)ML$\\sb{\\rm n}$. Variable-temperature $\\sp $C NMR studies and X-ray diffraction experiments on several of the mixed-metal clusters demonstrate that each of these compounds adopts a trans-bicapped octahedral configuration of metal atoms, i.e., the ML$\\sb{\\rm n}$ fragment symmetrically caps the triangular face opposite the unique Re(CO)$\\sb3$ group. The compound (HRe$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{2-}$ is a mixture of two isomers, which differ in the position of the hydride ligand on the metal framework.","A set of clusters (Re$\\sb7$C(CO)$\\sb{21}$HgY) $\\sp{2-}$ (Y = halide, pseudohalide, or hydrocarbyl) has also been prepared and characterized. Some of these compounds undergo ligand-exchange reactions of the type: (Re$\\sb7$C(CO)$\\sb{21}$HgY) $\\sp{2-}$ + YHgZ ${}\\sbsp{\\gets}{\\to}$ (Re$\\sb7$C(CO)$\\sb{21}$HgZ) $\\sp{2-}$ + HgY$\\sb2$. The position of the equilibrium depends on the electronic properties of Y and Z, with electron-withdrawing groups facilitating ligand redistribution.","The reaction of Re$\\sb2$(CO)$\\sb $ with sodium in a 1:1.2 molar ratio in triglyme at 200$\\sp\\circ$C yields the new rhenium carbido clusters (HRe$\\sb6$C(CO)$\\sb \\rbrack\\sp{3-}$ and (HRe$\\sb5$C(CO)$\\sb \\rbrack\\sp{2-}$. The former complex contains an octahedral arrangement of Re(CO)$\\sb3$ units; it reacts with transition metal electrophiles to give the mixed-metal clusters (HRe$\\sb6$C(CO)$\\sb $ML$\\sb{\\rm n}\\rbrack\\sp{2-}$. The latter cluster consists of a square-based pyramid of rhenium atoms with a $\\mu\\sb5$-carbido atom 0.10 A below the basal plane and a semibridging carbonyl on one basal-apical edge. This compound is the first example of such a M$\\sb5$C complex outside of the iron triad elements.","Made available in DSpace on 2014-12-15T23:19:10Z (GMT). No. of bitstreams: 1 8815352.pdf: 5911482 bytes, checksum: 19e070e0c4ca3526744f81cdc5a838ee (MD5) Previous issue date: 1988","Embargo set by: Seth Robbins for item 70565 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","193 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988."]},{"key":"dc:title","label":"Title","values":["Synthesis, Structure, and Reactivity of High-Nuclearity Carbido Clusters of Rhenium"]}]}],"canonical_facts":{"dc:contributor":["Shapley, John R."],"dc:creator":["Henly, Timothy James"],"dc:date":["2014-12-15T23:19:10Z","10000-01-01","1988"],"dc:description":["The cluster anion (Re$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{3-}$ reacts with late transition metal-based electrophiles to yield the mixed-metal clusters (Re$\\sb7$C(CO)$\\sb{21}$ML$\\sb{\\rm n}\\rbrack\\sp{2-}$ and with H$\\sp+$ to yield the hydrido species (HRe$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{2-}$. These complexes have been fully characterized by IR, $\\sp1$H NMR, and fast-atom bombardment mass spectroscopies. $\\sp1$H and $\\sp $C NMR, IR, and cyclic voltammetry studies on selected complexes indicate that the (Re$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{3-}$ cap is a poorer electron donor to the ML$\\sb{\\rm n}\\sp+$ moiety than the cyclopentadienide ligand in the analogous compounds $(\\eta\\sp5$-C$\\sb5$H$\\sb5$)ML$\\sb{\\rm n}$. Variable-temperature $\\sp $C NMR studies and X-ray diffraction experiments on several of the mixed-metal clusters demonstrate that each of these compounds adopts a trans-bicapped octahedral configuration of metal atoms, i.e., the ML$\\sb{\\rm n}$ fragment symmetrically caps the triangular face opposite the unique Re(CO)$\\sb3$ group. The compound (HRe$\\sb7$C(CO)$\\sb{21}\\rbrack\\sp{2-}$ is a mixture of two isomers, which differ in the position of the hydride ligand on the metal framework.","A set of clusters (Re$\\sb7$C(CO)$\\sb{21}$HgY) $\\sp{2-}$ (Y = halide, pseudohalide, or hydrocarbyl) has also been prepared and characterized. Some of these compounds undergo ligand-exchange reactions of the type: (Re$\\sb7$C(CO)$\\sb{21}$HgY) $\\sp{2-}$ + YHgZ ${}\\sbsp{\\gets}{\\to}$ (Re$\\sb7$C(CO)$\\sb{21}$HgZ) $\\sp{2-}$ + HgY$\\sb2$. The position of the equilibrium depends on the electronic properties of Y and Z, with electron-withdrawing groups facilitating ligand redistribution.","The reaction of Re$\\sb2$(CO)$\\sb $ with sodium in a 1:1.2 molar ratio in triglyme at 200$\\sp\\circ$C yields the new rhenium carbido clusters (HRe$\\sb6$C(CO)$\\sb \\rbrack\\sp{3-}$ and (HRe$\\sb5$C(CO)$\\sb \\rbrack\\sp{2-}$. The former complex contains an octahedral arrangement of Re(CO)$\\sb3$ units; it reacts with transition metal electrophiles to give the mixed-metal clusters (HRe$\\sb6$C(CO)$\\sb $ML$\\sb{\\rm n}\\rbrack\\sp{2-}$. The latter cluster consists of a square-based pyramid of rhenium atoms with a $\\mu\\sb5$-carbido atom 0.10 A below the basal plane and a semibridging carbonyl on one basal-apical edge. This compound is the first example of such a M$\\sb5$C complex outside of the iron triad elements.","Made available in DSpace on 2014-12-15T23:19:10Z (GMT). No. of bitstreams: 1 8815352.pdf: 5911482 bytes, checksum: 19e070e0c4ca3526744f81cdc5a838ee (MD5) Previous issue date: 1988","Embargo set by: Seth Robbins for item 70565 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","193 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988."],"dc:identifier":["http://hdl.handle.net/2142/70399","(UMI)AAI8815352"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Synthesis, Structure, and Reactivity of High-Nuclearity Carbido Clusters of Rhenium"],"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"}