{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70338"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70338","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The Effects of Main Group Elements on Transition Metal Carbonyl Clusters (Tellurium, Assembly, Chalcogen, Sulfur, Ditelluride)","abstract":"Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986.","abstract_html":"Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986.","abstract_has_math":false,"creators":["Bogan, Leonard E., Jr."],"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":"2014-12-15T23:18:46Z","date_published":"2014-12-15T23:18:46Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8701439"],"render_values":[{"text":"(UMI)AAI8701439","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70338","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Bogan, Leonard E., Jr."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:46Z","10000-01-01","1986"]},{"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/2142/70338","(UMI)AAI8701439"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986.","The reaction of Fe(,3)Te(,2)(CO)(,9) with metal carbonyl dimers at 150-180(DEGREES) and under 1300-1750 psi of CO was found to be a convenient route for the synthesis of a variety of transition metal - tellurium car- bonyl clusters. One of these, Cp(,2)Mo(,2)FeTe(,2)(CO)(,7) (Cp = (eta)('5)-C(,5)H(,5)), 3, generates a reactive intermediate upon heating to 110(DEGREES). This inter- mediate was trapped with Fe(CO)(,5), CpCo(CO)(,2), and RCCH (R = Ph, H). Assembly schemes are proposed which rationalize the observed structures of these and other four, five, and six-vertex cluster sys- tems. One of these schemes involves cluster rearrangement by ver- tex dissociation, and such dissociation of Fe(CO)(,x) (x < 5) fragments was shown to occur at 0(DEGREES) in the reaction of Cp(,2)Mo(,2)(CO)(,4) with Fe(,2)(S(,2))(CO)(,6).","The crystal structures of 3 (space group P(')1), Cp(,2)Mo(,2)Co(,2)Te(,3)- (CO)(,4) (space group P(')1), Cp(,2)Mo(,2)Fe(,2)Te(,2)(CO)(,7) (space group Pn2(,1)a),","Cp(,2)Mo(,2)Fe(Te(,2)Br)(CO)(,5) (space group P(')1; a = 8.614(6), b = 14.641 (10), c = 7.181(7) (ANGSTROM); (alpha) = 91.92(7), (beta) = 111.69(6), (gamma) = 99.34(6)(DEGREES);","Z = 2; D(calcd) = 2.782 g/mL; 3216 reflections refined to R(,F) = 0.0576 and R(,wF) = 0.0598), Cp(,2)Mo(,2)Fe(Te(,2)SC(S)NEt(,2))(CO)(,5) (space","group P2(,1)/c), and Cp(,2)Mo(,2)FeTe(,2)(CO)(,3)(C(,2)H(,2)) (space group P2(,1)/n) were solved. Interactions between main group atoms in these and","other M(,3)E(,2) clusters are discussed in terms of cluster geometry and valence electron count.","Cyclic voltammetry of Fe(,3)Te(,2)(CO)(,9-n)L(,n) (L = PPh(,3), n = 0, 1; L = PMe(,2)Ph, n = 0-3) and CpCoFeTe(,2)(CO)(,6) is reported and discussed in terms of ligand effects and charge delocalization in the clusters.","Oxidation of 3 with Br(,2)/CO gave a good yield of CpMoFe- (Te(,2)Br)(CO)(,5), which features a novel Te(,2)Br ligand. In solution the compound undergoes rapid exchange of Br making the Te atoms equivalent, but at -88(DEGREES) in toluene this exchange is slowed enough that ('1)H NMR indicates a chiral compound.","Reaction of (RC(,5)H(,4))MoFe(Te(,2)Br)(CO)(,5) (R = Me, i-Pr) with AgSb- F(,6) generated (RC(,5)H(,4))MoFe(Te(,2))(CO)(,5) SbF(,6). The cation reacted with a variety of nucleophiles (Br('-), Et(,2)NCS(,2)('-), HCOO('-), H('-), PMe(,2)Ph) to give compounds which apparently result from attack at Te.","Made available in DSpace on 2014-12-15T23:18:46Z (GMT). No. of bitstreams: 1 8701439.pdf: 5090861 bytes, checksum: 715def437b855bb364fb29aea64b3572 (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70504 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","167 p."]},{"key":"dc:title","label":"Title","values":["The Effects of Main Group Elements on Transition Metal Carbonyl Clusters (Tellurium, Assembly, Chalcogen, Sulfur, Ditelluride)"]}]}],"canonical_facts":{"dc:creator":["Bogan, Leonard E., Jr."],"dc:date":["2014-12-15T23:18:46Z","10000-01-01","1986"],"dc:description":["Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986.","The reaction of Fe(,3)Te(,2)(CO)(,9) with metal carbonyl dimers at 150-180(DEGREES) and under 1300-1750 psi of CO was found to be a convenient route for the synthesis of a variety of transition metal - tellurium car- bonyl clusters. One of these, Cp(,2)Mo(,2)FeTe(,2)(CO)(,7) (Cp = (eta)('5)-C(,5)H(,5)), 3, generates a reactive intermediate upon heating to 110(DEGREES). This inter- mediate was trapped with Fe(CO)(,5), CpCo(CO)(,2), and RCCH (R = Ph, H). Assembly schemes are proposed which rationalize the observed structures of these and other four, five, and six-vertex cluster sys- tems. One of these schemes involves cluster rearrangement by ver- tex dissociation, and such dissociation of Fe(CO)(,x) (x < 5) fragments was shown to occur at 0(DEGREES) in the reaction of Cp(,2)Mo(,2)(CO)(,4) with Fe(,2)(S(,2))(CO)(,6).","The crystal structures of 3 (space group P(')1), Cp(,2)Mo(,2)Co(,2)Te(,3)- (CO)(,4) (space group P(')1), Cp(,2)Mo(,2)Fe(,2)Te(,2)(CO)(,7) (space group Pn2(,1)a),","Cp(,2)Mo(,2)Fe(Te(,2)Br)(CO)(,5) (space group P(')1; a = 8.614(6), b = 14.641 (10), c = 7.181(7) (ANGSTROM); (alpha) = 91.92(7), (beta) = 111.69(6), (gamma) = 99.34(6)(DEGREES);","Z = 2; D(calcd) = 2.782 g/mL; 3216 reflections refined to R(,F) = 0.0576 and R(,wF) = 0.0598), Cp(,2)Mo(,2)Fe(Te(,2)SC(S)NEt(,2))(CO)(,5) (space","group P2(,1)/c), and Cp(,2)Mo(,2)FeTe(,2)(CO)(,3)(C(,2)H(,2)) (space group P2(,1)/n) were solved. Interactions between main group atoms in these and","other M(,3)E(,2) clusters are discussed in terms of cluster geometry and valence electron count.","Cyclic voltammetry of Fe(,3)Te(,2)(CO)(,9-n)L(,n) (L = PPh(,3), n = 0, 1; L = PMe(,2)Ph, n = 0-3) and CpCoFeTe(,2)(CO)(,6) is reported and discussed in terms of ligand effects and charge delocalization in the clusters.","Oxidation of 3 with Br(,2)/CO gave a good yield of CpMoFe- (Te(,2)Br)(CO)(,5), which features a novel Te(,2)Br ligand. In solution the compound undergoes rapid exchange of Br making the Te atoms equivalent, but at -88(DEGREES) in toluene this exchange is slowed enough that ('1)H NMR indicates a chiral compound.","Reaction of (RC(,5)H(,4))MoFe(Te(,2)Br)(CO)(,5) (R = Me, i-Pr) with AgSb- F(,6) generated (RC(,5)H(,4))MoFe(Te(,2))(CO)(,5) SbF(,6). The cation reacted with a variety of nucleophiles (Br('-), Et(,2)NCS(,2)('-), HCOO('-), H('-), PMe(,2)Ph) to give compounds which apparently result from attack at Te.","Made available in DSpace on 2014-12-15T23:18:46Z (GMT). No. of bitstreams: 1 8701439.pdf: 5090861 bytes, checksum: 715def437b855bb364fb29aea64b3572 (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70504 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","167 p."],"dc:identifier":["http://hdl.handle.net/2142/70338","(UMI)AAI8701439"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["The Effects of Main Group Elements on Transition Metal Carbonyl Clusters (Tellurium, Assembly, Chalcogen, Sulfur, Ditelluride)"],"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"}