{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/54492"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/54492","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"The in situ synthesis of supported ruthenium carbonyls","abstract":"The compound Ru⁺²(CO)₃Cl₂(THF) spontaneously adsorbs onto MgO, Al₂O₃, SiO₂, and NaY zeolite from THF solution evolving less than 0.1 equivalent of CO to yield a light yellow supported complex. Based on reaction stoichiometry, CO evolution and in situ infrared spectroscopy, the adsorption was found to produce two different surface-bound species depending on the support used. On SiO₂ and NaY zeolite, the surface species Ru⁺²(CO)₃Cl₂(SURFACE) is formed by a ligand substitution of THF for a surface hydroxyl group. When the adsorption is performed on MgO or AI₂O₃, the inorganic oxide acts as a chloride acceptor to form the surface species Ru⁺²(CO)₃(SURFACE)₃. A molecular analog of the adsorbed species Ru(CO)₃Cl₂(SURFACE) was synthesized and characterized by infrared spectroscopy, ¹H NMR, and an X-ray crystal structure. The infrared spectra of the adsorbed species, Ru(CO)₃Cl₂(SURFACE), and the model compound were in close agreement. Model compounds of Ru(CO)₃(SURFACE)₃ were also synthesized: however, these could not be structurally characterized. The reactivity of the adsorbed species, Ru(CO)₃Cl₂(SURFACE) and Ru(CO)₃(SURFACE)₃, towards the formation of supported bimetallics, polynuclear ruthenium carbonyl clusters, and ruthenium bipyridine coordination compounds was investigated. On SiO₂ and NaY zeolite, the chemistry of Ru(CO)₃Cl₂(SURFACE) paralleled that of Ru(CO)₃Cl₂(THF) in solution. On Al₂O₃ and MgO, the chemistry of Ru(CO)₃(SURFACE), was indicative of an adsorbed ruthenium carbonyl-containing no chloride ligands. The bimetallic cluster RuCo₃(CO)₁₂⁻ was synthesized on hydroxylated Al₂O₃ by the disproportionation of RuCo₂(CO)₁₁. The trimeric cluster RuCo₂(CO)₁₁ is spontaneously adsorbed onto AI₂O₃ from a pentane solution yielding the adsorbed species \"RuCo₂(CO)₁₀\", this was then transformed to the tetrameric cluster RuCo₃(CO)₁₂⁻ by the addition of THF. The adsorbed cluster anion RuCo₃(CO)₁₂⁻ could also be synthesized on AI₂O₃ by the deprotonation of the hydridic cluster HRuCo₃(CO)₁₂. Depending on the route, infrared evidence suggests formation of a solvated or unsolvated anion on the surface.","abstract_html":"The compound Ru⁺²(CO)₃Cl₂(THF) spontaneously adsorbs onto MgO, Al₂O₃, SiO₂, and NaY zeolite from THF solution evolving less than 0.1 equivalent of CO to yield a light yellow supported complex. Based on reaction stoichiometry, CO evolution and in situ infrared spectroscopy, the adsorption was found to produce two different surface-bound species depending on the support used. On SiO₂ and NaY zeolite, the surface species Ru⁺²(CO)₃Cl₂(SURFACE) is formed by a ligand substitution of THF for a surface hydroxyl group. When the adsorption is performed on MgO or AI₂O₃, the inorganic oxide acts as a chloride acceptor to form the surface species Ru⁺²(CO)₃(SURFACE)₃. A molecular analog of the adsorbed species Ru(CO)₃Cl₂(SURFACE) was synthesized and characterized by infrared spectroscopy, ¹H NMR, and an X-ray crystal structure. The infrared spectra of the adsorbed species, Ru(CO)₃Cl₂(SURFACE), and the model compound were in close agreement. Model compounds of Ru(CO)₃(SURFACE)₃ were also synthesized: however, these could not be structurally characterized. The reactivity of the adsorbed species, Ru(CO)₃Cl₂(SURFACE) and Ru(CO)₃(SURFACE)₃, towards the formation of supported bimetallics, polynuclear ruthenium carbonyl clusters, and ruthenium bipyridine coordination compounds was investigated. On SiO₂ and NaY zeolite, the chemistry of Ru(CO)₃Cl₂(SURFACE) paralleled that of Ru(CO)₃Cl₂(THF) in solution. On Al₂O₃ and MgO, the chemistry of Ru(CO)₃(SURFACE), was indicative of an adsorbed ruthenium carbonyl-containing no chloride ligands. The bimetallic cluster RuCo₃(CO)₁₂⁻ was synthesized on hydroxylated Al₂O₃ by the disproportionation of RuCo₂(CO)₁₁. The trimeric cluster RuCo₂(CO)₁₁ is spontaneously adsorbed onto AI₂O₃ from a pentane solution yielding the adsorbed species "RuCo₂(CO)₁₀", this was then transformed to the tetrameric cluster RuCo₃(CO)₁₂⁻ by the addition of THF. The adsorbed cluster anion RuCo₃(CO)₁₂⁻ could also be synthesized on AI₂O₃ by the deprotonation of the hydridic cluster HRuCo₃(CO)₁₂. Depending on the route, infrared evidence suggests formation of a solvated or unsolvated anion on the surface.","abstract_has_math":false,"creators":["Bergmeister, Joseph John"],"institution":"Virginia Polytechnic Institute and State University","degree_name":"Ph. D.","degree_level":"doctoral","degree_discipline":"Chemistry","degree_department":"Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":["Hanson, Brian E."],"committee_members":["Mason, John G.","Davis, Mark E.","Merola, Joseph S.","Wightman, James P."],"year":1989,"date_issued":"1989","date_published":"1989","updated_at":"2026-07-22T22:19:32Z","subjects":[],"languages":["en_US"],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10919/54492","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.committeechair","label":"Committee Chair","values":["Hanson, Brian E."]},{"key":"dc:contributor.committeemember","label":"Committee Member","values":["Mason, John G.","Davis, Mark E.","Merola, Joseph S.","Wightman, James P."]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Bergmeister, Joseph John"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2015-07-10T20:00:14Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2015-07-10T20:00:14Z"]},{"key":"dc:date.issued","label":"Date","values":["1989"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Polytechnic Institute and State University"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]},{"key":"dc:type.dcmitype","label":"Dc Type Dcmitype","values":["Text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph. D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Virginia Polytechnic Institute and State University"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en_US"]},{"key":"dc:rights","label":"Dc Rights","values":["In Copyright"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/vocab/InC/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10919/54492"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The compound Ru⁺²(CO)₃Cl₂(THF) spontaneously adsorbs onto MgO, Al₂O₃, SiO₂, and NaY zeolite from THF solution evolving less than 0.1 equivalent of CO to yield a light yellow supported complex. Based on reaction stoichiometry, CO evolution and in situ infrared spectroscopy, the adsorption was found to produce two different surface-bound species depending on the support used. On SiO₂ and NaY zeolite, the surface species Ru⁺²(CO)₃Cl₂(SURFACE) is formed by a ligand substitution of THF for a surface hydroxyl group. When the adsorption is performed on MgO or AI₂O₃, the inorganic oxide acts as a chloride acceptor to form the surface species Ru⁺²(CO)₃(SURFACE)₃. A molecular analog of the adsorbed species Ru(CO)₃Cl₂(SURFACE) was synthesized and characterized by infrared spectroscopy, ¹H NMR, and an X-ray crystal structure. The infrared spectra of the adsorbed species, Ru(CO)₃Cl₂(SURFACE), and the model compound were in close agreement. Model compounds of Ru(CO)₃(SURFACE)₃ were also synthesized: however, these could not be structurally characterized. The reactivity of the adsorbed species, Ru(CO)₃Cl₂(SURFACE) and Ru(CO)₃(SURFACE)₃, towards the formation of supported bimetallics, polynuclear ruthenium carbonyl clusters, and ruthenium bipyridine coordination compounds was investigated. On SiO₂ and NaY zeolite, the chemistry of Ru(CO)₃Cl₂(SURFACE) paralleled that of Ru(CO)₃Cl₂(THF) in solution. On Al₂O₃ and MgO, the chemistry of Ru(CO)₃(SURFACE), was indicative of an adsorbed ruthenium carbonyl-containing no chloride ligands. The bimetallic cluster RuCo₃(CO)₁₂⁻ was synthesized on hydroxylated Al₂O₃ by the disproportionation of RuCo₂(CO)₁₁. The trimeric cluster RuCo₂(CO)₁₁ is spontaneously adsorbed onto AI₂O₃ from a pentane solution yielding the adsorbed species \"RuCo₂(CO)₁₀\", this was then transformed to the tetrameric cluster RuCo₃(CO)₁₂⁻ by the addition of THF. The adsorbed cluster anion RuCo₃(CO)₁₂⁻ could also be synthesized on AI₂O₃ by the deprotonation of the hydridic cluster HRuCo₃(CO)₁₂. Depending on the route, infrared evidence suggests formation of a solvated or unsolvated anion on the surface."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph. D."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["The in situ synthesis of supported ruthenium carbonyls"]}]}],"canonical_facts":{"dc:contributor.committeechair":["Hanson, Brian E."],"dc:contributor.committeemember":["Mason, John G.","Davis, Mark E.","Merola, Joseph S.","Wightman, James P."],"dc:contributor.department":["Chemistry"],"dc:creator":["Bergmeister, Joseph John"],"dc:date.accessioned":["2015-07-10T20:00:14Z"],"dc:date.available":["2015-07-10T20:00:14Z"],"dc:date.issued":["1989"],"dc:description.abstract":["The compound Ru⁺²(CO)₃Cl₂(THF) spontaneously adsorbs onto MgO, Al₂O₃, SiO₂, and NaY zeolite from THF solution evolving less than 0.1 equivalent of CO to yield a light yellow supported complex. Based on reaction stoichiometry, CO evolution and in situ infrared spectroscopy, the adsorption was found to produce two different surface-bound species depending on the support used. On SiO₂ and NaY zeolite, the surface species Ru⁺²(CO)₃Cl₂(SURFACE) is formed by a ligand substitution of THF for a surface hydroxyl group. When the adsorption is performed on MgO or AI₂O₃, the inorganic oxide acts as a chloride acceptor to form the surface species Ru⁺²(CO)₃(SURFACE)₃. A molecular analog of the adsorbed species Ru(CO)₃Cl₂(SURFACE) was synthesized and characterized by infrared spectroscopy, ¹H NMR, and an X-ray crystal structure. The infrared spectra of the adsorbed species, Ru(CO)₃Cl₂(SURFACE), and the model compound were in close agreement. Model compounds of Ru(CO)₃(SURFACE)₃ were also synthesized: however, these could not be structurally characterized. The reactivity of the adsorbed species, Ru(CO)₃Cl₂(SURFACE) and Ru(CO)₃(SURFACE)₃, towards the formation of supported bimetallics, polynuclear ruthenium carbonyl clusters, and ruthenium bipyridine coordination compounds was investigated. On SiO₂ and NaY zeolite, the chemistry of Ru(CO)₃Cl₂(SURFACE) paralleled that of Ru(CO)₃Cl₂(THF) in solution. On Al₂O₃ and MgO, the chemistry of Ru(CO)₃(SURFACE), was indicative of an adsorbed ruthenium carbonyl-containing no chloride ligands. The bimetallic cluster RuCo₃(CO)₁₂⁻ was synthesized on hydroxylated Al₂O₃ by the disproportionation of RuCo₂(CO)₁₁. The trimeric cluster RuCo₂(CO)₁₁ is spontaneously adsorbed onto AI₂O₃ from a pentane solution yielding the adsorbed species \"RuCo₂(CO)₁₀\", this was then transformed to the tetrameric cluster RuCo₃(CO)₁₂⁻ by the addition of THF. The adsorbed cluster anion RuCo₃(CO)₁₂⁻ could also be synthesized on AI₂O₃ by the deprotonation of the hydridic cluster HRuCo₃(CO)₁₂. Depending on the route, infrared evidence suggests formation of a solvated or unsolvated anion on the surface."],"dc:description.degree":["Ph. D."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["http://hdl.handle.net/10919/54492"],"dc:language.iso":["en_US"],"dc:publisher":["Virginia Polytechnic Institute and State University"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:title":["The in situ synthesis of supported ruthenium carbonyls"],"dc:type":["Dissertation"],"dc:type.dcmitype":["Text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Ph. D."],"thesis:institution_name":["Virginia Polytechnic Institute and State University"]},"updated_at":"2026-07-22T22:19:32Z"}