{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70234"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70234","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis of Large Carbonyl Clusters of Ruthenium, Osmium and Rhenium","abstract":"The efficient preparation of several large anionic carbonyl clusters of ruthenium and osmium from M(,3)(CO)(,12) (M = Ru, Os) and sodium have been developed. Similar procedures have provided large anionic clusters of rhenium from Re(,2)(CO)(,10).","abstract_html":"The efficient preparation of several large anionic carbonyl clusters of ruthenium and osmium from M(,3)(CO)(,12) (M = Ru, Os) and sodium have been developed. Similar procedures have provided large anionic clusters of rhenium from Re(,2)(CO)(,10).","abstract_has_math":false,"creators":["Hayward, Chi-Mi Tai"],"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":"2014-12-15T23:18:02Z","date_published":"2014-12-15T23:18:02Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8409777"],"render_values":[{"text":"(UMI)AAI8409777","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70234","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Hayward, Chi-Mi Tai"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:02Z","10000-01-01","1984"]},{"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/2142/70234","(UMI)AAI8409777"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The efficient preparation of several large anionic carbonyl clusters of ruthenium and osmium from M(,3)(CO)(,12) (M = Ru, Os) and sodium have been developed. Similar procedures have provided large anionic clusters of rhenium from Re(,2)(CO)(,10).","The reaction of Ru(,3)(CO)(,12) and sodium in a 1:1 mole ratio affords Ru(,6)(CO)(,18)('2-) in refluxing tetrahydrofuran (66(DEGREES)C) but Ru(,6)C(CO)(,16)('2-) in refluxing diglyme (162(DEGREES)C). Under the latter conditions Ru(,6)(CO)(,18)('2-) is converted quantitatively to Ru(,6)C(CO)(,16)('2-) with the evolution of carbon dioxide, which has been trapped as barium carbonate. Treatment of Os(,3)(CO)(,12) with sodium (Os:Na = 1:1) in diglyme (150-160(DEGREES)C) provides Os(,6)(CO)(,18)('2-). Pyrolysis of Os(,6)(CO)(,18)('2-) in triglyme (216(DEGREES)C) gives Os(,10)C(CO)(,24)('2-) as the major product, which is formed also from the direct reaction of Os(,3)(CO)(,12) with sodium in tetraglyme at 230-260(DEGREES)C. Oxidation of Ru(,6)C(CO)(,16)('2-) and Os(,6)(CO)(,18)('2-) with aqueous ferric chloride in a carbon monoxide atmosphere produces Ru(,6)C(CO)(,17) and Os(,6)(CO)(,18) in good yields. A compound formulated as Os(,6)C(CO)(,17) is isolated in low yield from the similar oxidation of reaction mixtures produced upon pyrolysis of Os(,6)(CO)(,18)('2-). This is suggested as evidence for the formation of Os(,6)C(CO)(,16)('2-) under the conditions for conversion of Os(,6)(CO)(,18)('2-) to Os(,10)C(CO)(,24)('2-). Extended pyrolysis of Ru(,6)C(CO)(,16)('2-) also provides a decanuclear cluster, but Ru(,10)C(,2)(CO)(,24)('2-) has two carbide ligands. The structural analysis of Ru(,10)C(,2)(CO)(,24)('2-) shows the metal framework to be used on two essentially octahedral moieties fused at a common equatorial edge.","Treatment of Re(,2)(CO)(,10) with sodium (Re(,2):Na = 1:1) in diglyme at 150(DEGREES)C affords Re(,4)(CO)(,16)('2-), which in refluxing diglyme (162(DEGREES)C) is converted predominantly to H(,2)Re(,6)C(CO)(,18)('2-). In the latter transformation Re(,7)C(CO)(,21)('3-) and Re(,8)C(CO)(,24)('2-) are obtained as minor products. These clusters have been prepared selectively by employing the appropriate stoichiometric ratio of Re(,2)(CO)(,10) and sodium (Re(,2):Na = 3.5:3 for Re(,7)C and 4:2 for Re(,8)C) in triglyme (190-210(DEGREES)C). In both syntheses Re(,4)(CO)(,16)('2-) and then H(,2)Re(,6)C(CO)(,18)('2-) are the intermediates observed prior to the formation of product.","Made available in DSpace on 2014-12-15T23:18:02Z (GMT). No. of bitstreams: 1 8409777.pdf: 4247497 bytes, checksum: a0ae445c56417e362325a94e1a6a9ad6 (MD5) Previous issue date: 1984","Embargo set by: Seth Robbins for item 70400 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","138 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984."]},{"key":"dc:title","label":"Title","values":["Synthesis of Large Carbonyl Clusters of Ruthenium, Osmium and Rhenium"]}]}],"canonical_facts":{"dc:creator":["Hayward, Chi-Mi Tai"],"dc:date":["2014-12-15T23:18:02Z","10000-01-01","1984"],"dc:description":["The efficient preparation of several large anionic carbonyl clusters of ruthenium and osmium from M(,3)(CO)(,12) (M = Ru, Os) and sodium have been developed. Similar procedures have provided large anionic clusters of rhenium from Re(,2)(CO)(,10).","The reaction of Ru(,3)(CO)(,12) and sodium in a 1:1 mole ratio affords Ru(,6)(CO)(,18)('2-) in refluxing tetrahydrofuran (66(DEGREES)C) but Ru(,6)C(CO)(,16)('2-) in refluxing diglyme (162(DEGREES)C). Under the latter conditions Ru(,6)(CO)(,18)('2-) is converted quantitatively to Ru(,6)C(CO)(,16)('2-) with the evolution of carbon dioxide, which has been trapped as barium carbonate. Treatment of Os(,3)(CO)(,12) with sodium (Os:Na = 1:1) in diglyme (150-160(DEGREES)C) provides Os(,6)(CO)(,18)('2-). Pyrolysis of Os(,6)(CO)(,18)('2-) in triglyme (216(DEGREES)C) gives Os(,10)C(CO)(,24)('2-) as the major product, which is formed also from the direct reaction of Os(,3)(CO)(,12) with sodium in tetraglyme at 230-260(DEGREES)C. Oxidation of Ru(,6)C(CO)(,16)('2-) and Os(,6)(CO)(,18)('2-) with aqueous ferric chloride in a carbon monoxide atmosphere produces Ru(,6)C(CO)(,17) and Os(,6)(CO)(,18) in good yields. A compound formulated as Os(,6)C(CO)(,17) is isolated in low yield from the similar oxidation of reaction mixtures produced upon pyrolysis of Os(,6)(CO)(,18)('2-). This is suggested as evidence for the formation of Os(,6)C(CO)(,16)('2-) under the conditions for conversion of Os(,6)(CO)(,18)('2-) to Os(,10)C(CO)(,24)('2-). Extended pyrolysis of Ru(,6)C(CO)(,16)('2-) also provides a decanuclear cluster, but Ru(,10)C(,2)(CO)(,24)('2-) has two carbide ligands. The structural analysis of Ru(,10)C(,2)(CO)(,24)('2-) shows the metal framework to be used on two essentially octahedral moieties fused at a common equatorial edge.","Treatment of Re(,2)(CO)(,10) with sodium (Re(,2):Na = 1:1) in diglyme at 150(DEGREES)C affords Re(,4)(CO)(,16)('2-), which in refluxing diglyme (162(DEGREES)C) is converted predominantly to H(,2)Re(,6)C(CO)(,18)('2-). In the latter transformation Re(,7)C(CO)(,21)('3-) and Re(,8)C(CO)(,24)('2-) are obtained as minor products. These clusters have been prepared selectively by employing the appropriate stoichiometric ratio of Re(,2)(CO)(,10) and sodium (Re(,2):Na = 3.5:3 for Re(,7)C and 4:2 for Re(,8)C) in triglyme (190-210(DEGREES)C). In both syntheses Re(,4)(CO)(,16)('2-) and then H(,2)Re(,6)C(CO)(,18)('2-) are the intermediates observed prior to the formation of product.","Made available in DSpace on 2014-12-15T23:18:02Z (GMT). No. of bitstreams: 1 8409777.pdf: 4247497 bytes, checksum: a0ae445c56417e362325a94e1a6a9ad6 (MD5) Previous issue date: 1984","Embargo set by: Seth Robbins for item 70400 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","138 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984."],"dc:identifier":["http://hdl.handle.net/2142/70234","(UMI)AAI8409777"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Synthesis of Large Carbonyl Clusters of Ruthenium, Osmium and 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"}