{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/23693"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/23693","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Cyclopentadienyl ruthenium chalcogenides","abstract":"The interaction of transition metal complexes with H$\\sb2$S, SH$\\sp{-}$ and S$\\sbsp{2}{2-}$ ligands is of interest because of their chemical relevance to metal sulfide hydrodesulfurization (HDS) catalysts. Ruthenium sulfur complexes are of interest because of the favorable catalytic properties of RuS$\\sb2$ which can act as HDS catalyst as well as an electrocatalyst. The purpose of this thesis was to synthesize, characterize, and study the reactivity of ruthenium compounds containing SH, H$\\sb2$S and S$\\sbsp{2}{2-}$ ligands.","abstract_html":"The interaction of transition metal complexes with H$\\sb2$S, SH$\\sp{-}$ and S$\\sbsp{2}{2-}$ ligands is of interest because of their chemical relevance to metal sulfide hydrodesulfurization (HDS) catalysts. Ruthenium sulfur complexes are of interest because of the favorable catalytic properties of RuS$\\sb2$ which can act as HDS catalyst as well as an electrocatalyst. The purpose of this thesis was to synthesize, characterize, and study the reactivity of ruthenium compounds containing SH, H$\\sb2$S and S$\\sbsp{2}{2-}$ ligands.","abstract_has_math":true,"creators":["Amarasekera, Jayantha"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry, Inorganic","degree_department":null,"school":null,"contributors":["Rauchfuss, Thomas B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T14:23:33Z","date_published":"2011-05-07T14:23:33Z","updated_at":"2026-07-22T22:25:22Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1989 Amarasekera, Jayantha"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8916209","AAI8916209"],"render_values":[{"text":"(UMI)AAI8916209","href":null,"code":true},{"text":"AAI8916209","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/23693","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Rauchfuss, Thomas B."]},{"key":"dc:creator","label":"Author","values":["Amarasekera, Jayantha"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T14:23:33Z","10000-01-01","1989"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry, Inorganic"]},{"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":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1989 Amarasekera, Jayantha"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8916209","AAI8916209","http://hdl.handle.net/2142/23693"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The interaction of transition metal complexes with H$\\sb2$S, SH$\\sp{-}$ and S$\\sbsp{2}{2-}$ ligands is of interest because of their chemical relevance to metal sulfide hydrodesulfurization (HDS) catalysts. Ruthenium sulfur complexes are of interest because of the favorable catalytic properties of RuS$\\sb2$ which can act as HDS catalyst as well as an electrocatalyst. The purpose of this thesis was to synthesize, characterize, and study the reactivity of ruthenium compounds containing SH, H$\\sb2$S and S$\\sbsp{2}{2-}$ ligands.","The electron rich ruthenium hydrosulfide complex CpRu(PPh$\\sb3)\\sb2$SH (1) was synthesized from CpRu(PPh$\\sb3)\\sb2$Cl and NaSH. In contrast to the parent chloride, CpRu(PPh$\\sb3)\\sb2$Cl, 1 undergoes complete monocarbonylation to CpRu(PPh$\\sb3$)(CO)(SH). The complex 1 easily undergoes protonation to the H$\\sb2$S complex, (CpRu(PPh$\\sb3)\\sb2$(SH$\\sb2)\\rbrack\\sp{+}$ and alkylation to the thiol complex, (CpRu(PPh$\\sb3)\\sb2$(RSH)) $\\sp{+}$. These complexes can also prepared directly from the highly reactive CpRu(PPh$\\sb3)\\sb2$OTf (OTf = CF$\\sb3$SO$\\sb3)$ (2) and H$\\sb2$S and RSH respectively. The H$\\sb2$S complex is labile, and establishes an equilibrium with hydrogen involving the dihydride complex (CpRu(PPh$\\sb3)\\sb2$H$\\sb2\\rbrack\\sp{+}$.","Thermolysis of 1 in toluene forms the phosphine free Cp$\\sb4$Ru$\\sb4$S$\\sb4$. The solid state structure of (MeCp)$\\sb4$Ru$\\sb4$S$\\sb4$ consists of a distorted cubane configuration with two Ru-Ru bonds. The electron rich nature of this cubane is reflected in its electrochemistry which reveals two reversible one-electron oxidations.","Complex 1 undergoes a two electron oxidation to $\\lbrack$CpRu(PPh$\\sb3$)$\\sb2\\rbrack\\sb2$($\\mu$-S$\\sb2$)$\\sp{2+}$ (3) containing a bridging persulfide ligand. The structural and electrochemical properties of 3 suggest that the persulfide ligand serves as a powerful $\\pi$-donor to the ruthenium centers. The persulfide complex 3 can be easily reduced to the monocation $\\lbrack$CpRu(PPh$\\sb3$)$\\sb2\\rbrack\\sb2$($\\mu$-S$\\sb2$)$\\sp{+}$, but the neutral species is too reducing to be isolated. Complex 3 can also be prepared from 2 and elemental sulfur. The reaction of 2 with the sulfur transfer reagent, thiirane does not give 3, instead the thiirane complex $\\lbrack$CpRu(PPh$\\sb3$)$\\sb2$(SC$\\sb2$H$\\sb4$)$\\rbrack\\sp{+}$, which was structurally characterized.","The reaction of 1 with sulfur gave two ruthenium polysulfides, cyclo - $\\lbrack$CpRu(PPh$\\sb3$)$\\rbrack\\sb2$S$\\sb{\\rm x}$ (x = 4, 6). The structure of $\\lbrack$(MeCp)Ru(PPh$\\sb3$)$\\rbrack\\sb2$S$\\sb6$ consists of a bicyclic Ru$\\sb2$S$\\sb6$ core with short Ru-S bonds. These metal-sulfur multiple bonds induce a transannular bonding, similar to S$\\sbsp{8}{2+}$. The structure of ((MeCp)Ru(PPh$\\sb3$)) $\\sb2$S$\\sb4$ suggest a delocalized $\\pi$-network, and accordingly it shows rich electrochemistry. These $\\lbrack$CpRu(PPh$\\sb3$)$\\rbrack\\sb2$S$\\sb{\\rm x}$ (x = 4, 6) complexes can also be prepared from the reaction of $\\lbrack$Bu$\\sb4$N$\\rbrack\\sb2$S$\\sb6$ and 2 or 3.","The selenium analogue of 3 can be prepared from the reaction of CpRu(PPh$\\sb3$)$\\sb2$OTf and elemental selenium. The similar reaction of (MeCp)Ru(PPh$\\sb3$)$\\sb2$OTf and selenium gives $\\lbrack$(MeCp)Ru(PPh$\\sb3$)$\\rbrack\\sb2$Se$\\sbsp{4}{2+}$ as the major product, which contains a Ru$\\sb2$Se$\\sb4$ core with $\\eta\\sp1$, $\\eta\\sp2$ -Se$\\sb2$ ligands.","Made available in DSpace on 2011-05-07T14:23:33Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 8916209.pdf: 6604816 bytes, checksum: e4aa3dd8290fc397532f921fec6e7b77 (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:06:12Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:31:46-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Cyclopentadienyl ruthenium chalcogenides"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Amarasekera, Jayantha"],"dc:date":["2011-05-07T14:23:33Z","10000-01-01","1989"],"dc:description":["The interaction of transition metal complexes with H$\\sb2$S, SH$\\sp{-}$ and S$\\sbsp{2}{2-}$ ligands is of interest because of their chemical relevance to metal sulfide hydrodesulfurization (HDS) catalysts. Ruthenium sulfur complexes are of interest because of the favorable catalytic properties of RuS$\\sb2$ which can act as HDS catalyst as well as an electrocatalyst. The purpose of this thesis was to synthesize, characterize, and study the reactivity of ruthenium compounds containing SH, H$\\sb2$S and S$\\sbsp{2}{2-}$ ligands.","The electron rich ruthenium hydrosulfide complex CpRu(PPh$\\sb3)\\sb2$SH (1) was synthesized from CpRu(PPh$\\sb3)\\sb2$Cl and NaSH. In contrast to the parent chloride, CpRu(PPh$\\sb3)\\sb2$Cl, 1 undergoes complete monocarbonylation to CpRu(PPh$\\sb3$)(CO)(SH). The complex 1 easily undergoes protonation to the H$\\sb2$S complex, (CpRu(PPh$\\sb3)\\sb2$(SH$\\sb2)\\rbrack\\sp{+}$ and alkylation to the thiol complex, (CpRu(PPh$\\sb3)\\sb2$(RSH)) $\\sp{+}$. These complexes can also prepared directly from the highly reactive CpRu(PPh$\\sb3)\\sb2$OTf (OTf = CF$\\sb3$SO$\\sb3)$ (2) and H$\\sb2$S and RSH respectively. The H$\\sb2$S complex is labile, and establishes an equilibrium with hydrogen involving the dihydride complex (CpRu(PPh$\\sb3)\\sb2$H$\\sb2\\rbrack\\sp{+}$.","Thermolysis of 1 in toluene forms the phosphine free Cp$\\sb4$Ru$\\sb4$S$\\sb4$. The solid state structure of (MeCp)$\\sb4$Ru$\\sb4$S$\\sb4$ consists of a distorted cubane configuration with two Ru-Ru bonds. The electron rich nature of this cubane is reflected in its electrochemistry which reveals two reversible one-electron oxidations.","Complex 1 undergoes a two electron oxidation to $\\lbrack$CpRu(PPh$\\sb3$)$\\sb2\\rbrack\\sb2$($\\mu$-S$\\sb2$)$\\sp{2+}$ (3) containing a bridging persulfide ligand. The structural and electrochemical properties of 3 suggest that the persulfide ligand serves as a powerful $\\pi$-donor to the ruthenium centers. The persulfide complex 3 can be easily reduced to the monocation $\\lbrack$CpRu(PPh$\\sb3$)$\\sb2\\rbrack\\sb2$($\\mu$-S$\\sb2$)$\\sp{+}$, but the neutral species is too reducing to be isolated. Complex 3 can also be prepared from 2 and elemental sulfur. The reaction of 2 with the sulfur transfer reagent, thiirane does not give 3, instead the thiirane complex $\\lbrack$CpRu(PPh$\\sb3$)$\\sb2$(SC$\\sb2$H$\\sb4$)$\\rbrack\\sp{+}$, which was structurally characterized.","The reaction of 1 with sulfur gave two ruthenium polysulfides, cyclo - $\\lbrack$CpRu(PPh$\\sb3$)$\\rbrack\\sb2$S$\\sb{\\rm x}$ (x = 4, 6). The structure of $\\lbrack$(MeCp)Ru(PPh$\\sb3$)$\\rbrack\\sb2$S$\\sb6$ consists of a bicyclic Ru$\\sb2$S$\\sb6$ core with short Ru-S bonds. These metal-sulfur multiple bonds induce a transannular bonding, similar to S$\\sbsp{8}{2+}$. The structure of ((MeCp)Ru(PPh$\\sb3$)) $\\sb2$S$\\sb4$ suggest a delocalized $\\pi$-network, and accordingly it shows rich electrochemistry. These $\\lbrack$CpRu(PPh$\\sb3$)$\\rbrack\\sb2$S$\\sb{\\rm x}$ (x = 4, 6) complexes can also be prepared from the reaction of $\\lbrack$Bu$\\sb4$N$\\rbrack\\sb2$S$\\sb6$ and 2 or 3.","The selenium analogue of 3 can be prepared from the reaction of CpRu(PPh$\\sb3$)$\\sb2$OTf and elemental selenium. The similar reaction of (MeCp)Ru(PPh$\\sb3$)$\\sb2$OTf and selenium gives $\\lbrack$(MeCp)Ru(PPh$\\sb3$)$\\rbrack\\sb2$Se$\\sbsp{4}{2+}$ as the major product, which contains a Ru$\\sb2$Se$\\sb4$ core with $\\eta\\sp1$, $\\eta\\sp2$ -Se$\\sb2$ ligands.","Made available in DSpace on 2011-05-07T14:23:33Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 8916209.pdf: 6604816 bytes, checksum: e4aa3dd8290fc397532f921fec6e7b77 (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:06:12Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:31:46-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["(UMI)AAI8916209","AAI8916209","http://hdl.handle.net/2142/23693"],"dc:language":["eng"],"dc:rights":["Copyright 1989 Amarasekera, Jayantha"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Cyclopentadienyl ruthenium chalcogenides"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry, Inorganic"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:22Z"}