{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70317"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70317","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The Chemistry of Triruthenium Hydrocarbyls (Metal Clusters)","abstract":"The triruthenium methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH), was prepared by a hydride addition/protonation sequence from HRu(,3)(CO)(,10)((mu)-COCH(,3)). Variable temperature ('1)H and ('13)C NMR experiments suggest the intermediacy of a formyl complex, presumably HRu(,3)(CO)(,9)(C(H)O)((mu)-COCH(,3))('-) , in the preparation of HRu(,3)(CO)(,10)((mu)(,3)-CH). The methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH), rearranges rapidly (-10(DEGREES)C) to the isomeric carbonylmethylidyne cluster, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO), via intramolecular coupling of the carbyne ligand and a cluster-bound carbonyl. Hydrogenation of H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO) yields H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CH), demonstrating that this C-C coupling process is reversible.","abstract_html":"The triruthenium methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH), was prepared by a hydride addition/protonation sequence from HRu(,3)(CO)(,10)((mu)-COCH(,3)). Variable temperature ('1)H and ('13)C NMR experiments suggest the intermediacy of a formyl complex, presumably HRu(,3)(CO)(,9)(C(H)O)((mu)-COCH(,3))('-) , in the preparation of HRu(,3)(CO)(,10)((mu)(,3)-CH). The methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH), rearranges rapidly (-10(DEGREES)C) to the isomeric carbonylmethylidyne cluster, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO), via intramolecular coupling of the carbyne ligand and a cluster-bound carbonyl. Hydrogenation of H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO) yields H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CH), demonstrating that this C-C coupling process is reversible.","abstract_has_math":false,"creators":["Holmgren, Jennifer Salem"],"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":"2014-12-15T23:18:36Z","date_published":"2014-12-15T23:18:36Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8610940"],"render_values":[{"text":"(UMI)AAI8610940","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70317","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Holmgren, Jennifer Salem"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:36Z","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/2142/70317","(UMI)AAI8610940"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The triruthenium methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH), was prepared by a hydride addition/protonation sequence from HRu(,3)(CO)(,10)((mu)-COCH(,3)). Variable temperature ('1)H and ('13)C NMR experiments suggest the intermediacy of a formyl complex, presumably HRu(,3)(CO)(,9)(C(H)O)((mu)-COCH(,3))('-) , in the preparation of HRu(,3)(CO)(,10)((mu)(,3)-CH). The methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH), rearranges rapidly (-10(DEGREES)C) to the isomeric carbonylmethylidyne cluster, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO), via intramolecular coupling of the carbyne ligand and a cluster-bound carbonyl. Hydrogenation of H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO) yields H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CH), demonstrating that this C-C coupling process is reversible.","The carbonylmethylidyne cluster, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO), is reduced to the vinylidene cluster, H(,2)Ru(,3)(CO)(,9)((mu)-CCH(,2)), with BH(,3)(.)THF. The carbonylmethylidyne cluster, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO), reacts with nucleophiles at the apical carbon atom. Reaction with MeOH or H(,2)O provides H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CC(O)OMe) and H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CC(O)OH), respectively. A hydride addition/protonation sequence from the carbonylmethylidyne, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO), gives the formylmethylidyne complex, H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CC(O)H). The latter reacts with H(,2) to give the ethylidyne cluster, H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CCH(,3)).","The triruthenium methylene cluster, Ru(,3)(CO)(,10)((mu)-CO)((mu)-CH(,2)), is prepared by the reaction of diazomethane and Ru(,3)(CO)(,12). Reactivity studies point to facile C-C bond formation involving the cluster bound methylene and added diazomethane or added CO. Reaction with added methylene provides the H(,2)Ru(,3)(CO)(,9)((mu)-CCH(,2)) while reaction with CO provides Ru(,3)(CO)(,12) and ketene. The methylene cluster, Ru(,3)(CO)(,10)((mu)-CO)((mu)-CH(,2)), thermally rearranges to the carbonylmethylidyne cluster, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO). This rearrangement probably involves the previously discussed methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH). The trimethylsilyl substituted alkylidene cluster, Ru(,3)(CO)(,10)((mu)-CO)((mu)-CH(,2)), has also been prepared and its reactivity investigated.","Spin saturation transfer experiments on Ru(,3)(CO)(,10)((mu)-CO)((mu)-CH(,2)) suggest that the methylene unit can move over the cluster face, presumably via a bridge-to-terminal isomerization process.","Reaction of diazomethane with the phosphine substituted triruthenium cluster, Ru(,3)(CO)(,10)(dppm), yields the novel cluster, Ru(,3)(CO)(,7)((eta)('3)-(C,C,O),(mu)(,3)-COCH(,2))((mu)-CH(,2))(dppm). This cluster was characterized spectroscopically as well as by a single crystal X-ray diffraction study. The cluster contains a ketene ligand and a bridging methylene ligand. Surprisingly, each of the three atoms in the C-C-O unit, the ketene ligand, is bound to a different metal atom in the cluster. On addition of CO, the ketene and methylene ligands in Ru(,3)(CO)(,7)((eta)('3)-(C,C,O),(mu)(,3)-COCH(,2))((mu)-CH(,2))(dppm) couple to form an oxaallyl unit, while the triruthenium cluster degrades to a ruthenium dimer, Ru(,2)(CO)(,5)((eta)('4)-(C,C,C,O),(mu)-CH(,2)C(O)CH(,2))(dppm), which was characterized by single crystal X-ray diffraction.","Made available in DSpace on 2014-12-15T23:18:36Z (GMT). No. of bitstreams: 1 8610940.pdf: 6909590 bytes, checksum: 921f69b3fb0f069a39bf018d29092be0 (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70483 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","211 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986."]},{"key":"dc:title","label":"Title","values":["The Chemistry of Triruthenium Hydrocarbyls (Metal Clusters)"]}]}],"canonical_facts":{"dc:creator":["Holmgren, Jennifer Salem"],"dc:date":["2014-12-15T23:18:36Z","10000-01-01","1986"],"dc:description":["The triruthenium methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH), was prepared by a hydride addition/protonation sequence from HRu(,3)(CO)(,10)((mu)-COCH(,3)). Variable temperature ('1)H and ('13)C NMR experiments suggest the intermediacy of a formyl complex, presumably HRu(,3)(CO)(,9)(C(H)O)((mu)-COCH(,3))('-) , in the preparation of HRu(,3)(CO)(,10)((mu)(,3)-CH). The methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH), rearranges rapidly (-10(DEGREES)C) to the isomeric carbonylmethylidyne cluster, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO), via intramolecular coupling of the carbyne ligand and a cluster-bound carbonyl. Hydrogenation of H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO) yields H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CH), demonstrating that this C-C coupling process is reversible.","The carbonylmethylidyne cluster, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO), is reduced to the vinylidene cluster, H(,2)Ru(,3)(CO)(,9)((mu)-CCH(,2)), with BH(,3)(.)THF. The carbonylmethylidyne cluster, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO), reacts with nucleophiles at the apical carbon atom. Reaction with MeOH or H(,2)O provides H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CC(O)OMe) and H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CC(O)OH), respectively. A hydride addition/protonation sequence from the carbonylmethylidyne, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO), gives the formylmethylidyne complex, H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CC(O)H). The latter reacts with H(,2) to give the ethylidyne cluster, H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CCH(,3)).","The triruthenium methylene cluster, Ru(,3)(CO)(,10)((mu)-CO)((mu)-CH(,2)), is prepared by the reaction of diazomethane and Ru(,3)(CO)(,12). Reactivity studies point to facile C-C bond formation involving the cluster bound methylene and added diazomethane or added CO. Reaction with added methylene provides the H(,2)Ru(,3)(CO)(,9)((mu)-CCH(,2)) while reaction with CO provides Ru(,3)(CO)(,12) and ketene. The methylene cluster, Ru(,3)(CO)(,10)((mu)-CO)((mu)-CH(,2)), thermally rearranges to the carbonylmethylidyne cluster, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO). This rearrangement probably involves the previously discussed methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH). The trimethylsilyl substituted alkylidene cluster, Ru(,3)(CO)(,10)((mu)-CO)((mu)-CH(,2)), has also been prepared and its reactivity investigated.","Spin saturation transfer experiments on Ru(,3)(CO)(,10)((mu)-CO)((mu)-CH(,2)) suggest that the methylene unit can move over the cluster face, presumably via a bridge-to-terminal isomerization process.","Reaction of diazomethane with the phosphine substituted triruthenium cluster, Ru(,3)(CO)(,10)(dppm), yields the novel cluster, Ru(,3)(CO)(,7)((eta)('3)-(C,C,O),(mu)(,3)-COCH(,2))((mu)-CH(,2))(dppm). This cluster was characterized spectroscopically as well as by a single crystal X-ray diffraction study. The cluster contains a ketene ligand and a bridging methylene ligand. Surprisingly, each of the three atoms in the C-C-O unit, the ketene ligand, is bound to a different metal atom in the cluster. On addition of CO, the ketene and methylene ligands in Ru(,3)(CO)(,7)((eta)('3)-(C,C,O),(mu)(,3)-COCH(,2))((mu)-CH(,2))(dppm) couple to form an oxaallyl unit, while the triruthenium cluster degrades to a ruthenium dimer, Ru(,2)(CO)(,5)((eta)('4)-(C,C,C,O),(mu)-CH(,2)C(O)CH(,2))(dppm), which was characterized by single crystal X-ray diffraction.","Made available in DSpace on 2014-12-15T23:18:36Z (GMT). No. of bitstreams: 1 8610940.pdf: 6909590 bytes, checksum: 921f69b3fb0f069a39bf018d29092be0 (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70483 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","211 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986."],"dc:identifier":["http://hdl.handle.net/2142/70317","(UMI)AAI8610940"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["The Chemistry of Triruthenium Hydrocarbyls (Metal Clusters)"],"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"}