{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70424"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70424","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Organometallic and Inorganic Derivatives of the Tetrathiometallates","abstract":"In an effort to study the tetrathiometallates as ligands in heterometallic complexes, which may bind $\\pi$-acidic coligands, the preparation of a number of low-valent organometallic derivatives of MoS$\\sb4\\sp{2-}$ and WS$\\sb4\\sp{2-}$ was undertaken. The complex ((COD)Rh) $\\sb2$WS$\\sb4$ 1 was prepared from the direct reaction of equimolar amounts of ((COD)RhCl) $\\sb2$ and (Ph$\\sb4$P)$\\sb2$WS$\\sb4$. Compound 1 was found to exhibit extensive ligand substitution chemistry, involving organophosphines, CO, and $t$-BuNC. It was found that 1 could only support two strongly $\\pi$-acidic CO ligands; ((PPh$\\sb3$)(CO)Rh) $\\sb2$WS$\\sb4$ was found to be the stable species. The reaction of Pd(WS$\\sb4)\\sb2\\sp{2-}$ with an equimolar amount of ((COD)RhCl) $\\sb2$ gave the insoluble species, (COD)Rh($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Pd($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Rh(COD). This complex reacted with excess PPh$\\sb3$, giving the CH$\\sb2$Cl$\\sb2$-soluble species: (PPh$\\sb3)\\sb2$Rh($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Pd($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Rh(PPh$\\sb3)\\sb2$.","abstract_html":"In an effort to study the tetrathiometallates as ligands in heterometallic complexes, which may bind <span class=\"etd-inline-math\">&pi;</span>-acidic coligands, the preparation of a number of low-valent organometallic derivatives of MoS$\\sb4\\sp{2-}$ and WS$\\sb4\\sp{2-}$ was undertaken. The complex ((COD)Rh) $\\sb2$WS$\\sb4$ 1 was prepared from the direct reaction of equimolar amounts of ((COD)RhCl) $\\sb2$ and (Ph$\\sb4$P)$\\sb2$WS$\\sb4$. Compound 1 was found to exhibit extensive ligand substitution chemistry, involving organophosphines, CO, and $t$-BuNC. It was found that 1 could only support two strongly <span class=\"etd-inline-math\">&pi;</span>-acidic CO ligands; ((PPh$\\sb3$)(CO)Rh) $\\sb2$WS$\\sb4$ was found to be the stable species. The reaction of Pd(WS$\\sb4)\\sb2\\sp{2-}$ with an equimolar amount of ((COD)RhCl) $\\sb2$ gave the insoluble species, (COD)Rh(<span class=\"etd-inline-math\">&mu;</span>-S)$\\sb2$W(<span class=\"etd-inline-math\">&mu;</span>-S)$\\sb2$Pd(<span class=\"etd-inline-math\">&mu;</span>-S)$\\sb2$W(<span class=\"etd-inline-math\">&mu;</span>-S)$\\sb2$Rh(COD). This complex reacted with excess PPh$\\sb3$, giving the CH$\\sb2$Cl$\\sb2$-soluble species: (PPh$\\sb3)\\sb2$Rh(<span class=\"etd-inline-math\">&mu;</span>-S)$\\sb2$W(<span class=\"etd-inline-math\">&mu;</span>-S)$\\sb2$Pd(<span class=\"etd-inline-math\">&mu;</span>-S)$\\sb2$W(<span class=\"etd-inline-math\">&mu;</span>-S)$\\sb2$Rh(PPh$\\sb3)\\sb2$.","abstract_has_math":true,"creators":["Howard, Kevin Edward"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Rauchfuss, Thomas B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:19:23Z","date_published":"2014-12-15T23:19:23Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8908710"],"render_values":[{"text":"(UMI)AAI8908710","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70424","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":["Howard, Kevin Edward"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:19:23Z","10000-01-01","1988"]},{"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/2142/70424","(UMI)AAI8908710"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["In an effort to study the tetrathiometallates as ligands in heterometallic complexes, which may bind $\\pi$-acidic coligands, the preparation of a number of low-valent organometallic derivatives of MoS$\\sb4\\sp{2-}$ and WS$\\sb4\\sp{2-}$ was undertaken. The complex ((COD)Rh) $\\sb2$WS$\\sb4$ 1 was prepared from the direct reaction of equimolar amounts of ((COD)RhCl) $\\sb2$ and (Ph$\\sb4$P)$\\sb2$WS$\\sb4$. Compound 1 was found to exhibit extensive ligand substitution chemistry, involving organophosphines, CO, and $t$-BuNC. It was found that 1 could only support two strongly $\\pi$-acidic CO ligands; ((PPh$\\sb3$)(CO)Rh) $\\sb2$WS$\\sb4$ was found to be the stable species. The reaction of Pd(WS$\\sb4)\\sb2\\sp{2-}$ with an equimolar amount of ((COD)RhCl) $\\sb2$ gave the insoluble species, (COD)Rh($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Pd($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Rh(COD). This complex reacted with excess PPh$\\sb3$, giving the CH$\\sb2$Cl$\\sb2$-soluble species: (PPh$\\sb3)\\sb2$Rh($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Pd($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Rh(PPh$\\sb3)\\sb2$.","Complexes of general formula (($\\eta\\sp5$-C$\\sb5$H$\\sb4$R)Ru(PPh$\\sb3$)) $\\sb2$ME$\\sb4$ (where R = H, CH$\\sb3$; M = Mo, W; E = S, Se) were synthesized from two equivalents of ($\\eta\\sp5$-C$\\sb5$H$\\sb4$R)Ru(PPh$\\sb3)\\sb2$Cl and one equivalent of the corresponding (Ph$\\sb4$P)$\\sb2$ME$\\sb4$. The WSe$\\sb4$ derivative was prepared using ($t$-BuNH$\\sb3)\\sb2$WSe$\\sb4$, which was obtained from the reaction of W(NH-$t$-Bu)$\\sb2$(N-$t$-Bu)$\\sb2$ with H$\\sb2$Se. These compounds undergo single one electron oxidations in their cyclic voltammograms. Trialkylphosphines, carbon monoxide, and isocyanides (RNC, R = $t$-Bu, Me, and Bz) were found to displace the PPh$\\sb3$ ligands in (CpRu(PPh$\\sb3$)) $\\sb2$WS$\\sb4$ 2. In the case of CO however, substitution was observed to occur at only one ruthenium center. A kinetic study of the substitution of PPh$\\sb3$ by $t$-BuNC in 2 revealed that the rate was independent of ($t$-BuNC), indicating a dissociative mechanism.","A number of (L$\\sb{\\rm n}$M$\\sp\\prime$) $\\sb2$WS$\\sb4$ complexes were prepared from WS$\\sb4\\sp{2-}$ and compounds of the type (L$\\sb{\\rm n}$M($\\mu$-Cl)) $\\sb2$. These included complexes where L$\\sb{\\rm n}$M was (NBD)Rh, (COD)Ir, ($\\eta\\sp5$-C$\\sb5$Me$\\sb5$)RhCl, and (allyl)Pd. The Rh(III) and Pd(II) derivatives were characterized by X-ray crystallography which showed M-W distances of 2.90A(av.) and 2.80A(av.) respectively. Poorly soluble complexes of the type (COD)PtMS$\\sb4$ (M = Mo, W) were prepared from the reaction of (COD)PtCl$\\sb2$ and (Ph$\\sb4$P)$\\sb2$MS$\\sb4$. The thermal gravimetric analyses of ((COD)Rh) $\\sb2$MS$\\sb4$ and (COD)PtMS$\\sb4$ over temperature ranges of 50-900$\\sp\\circ$C indicate the formation of MRh$\\sb2$S$\\sb{\\rm x}$ (x = 2 or 2.5) and PtMS formulas. We suggest that these complexes should be examined as precursors to new ternary metal sulfides. (Abstract shortened with permission of author.)","Made available in DSpace on 2014-12-15T23:19:23Z (GMT). No. of bitstreams: 1 8908710.pdf: 5167483 bytes, checksum: 4533f5c86c2cb6c05a24e6b4786f8837 (MD5) Previous issue date: 1988","Embargo set by: Seth Robbins for item 70590 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","158 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988."]},{"key":"dc:title","label":"Title","values":["Organometallic and Inorganic Derivatives of the Tetrathiometallates"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Howard, Kevin Edward"],"dc:date":["2014-12-15T23:19:23Z","10000-01-01","1988"],"dc:description":["In an effort to study the tetrathiometallates as ligands in heterometallic complexes, which may bind $\\pi$-acidic coligands, the preparation of a number of low-valent organometallic derivatives of MoS$\\sb4\\sp{2-}$ and WS$\\sb4\\sp{2-}$ was undertaken. The complex ((COD)Rh) $\\sb2$WS$\\sb4$ 1 was prepared from the direct reaction of equimolar amounts of ((COD)RhCl) $\\sb2$ and (Ph$\\sb4$P)$\\sb2$WS$\\sb4$. Compound 1 was found to exhibit extensive ligand substitution chemistry, involving organophosphines, CO, and $t$-BuNC. It was found that 1 could only support two strongly $\\pi$-acidic CO ligands; ((PPh$\\sb3$)(CO)Rh) $\\sb2$WS$\\sb4$ was found to be the stable species. The reaction of Pd(WS$\\sb4)\\sb2\\sp{2-}$ with an equimolar amount of ((COD)RhCl) $\\sb2$ gave the insoluble species, (COD)Rh($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Pd($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Rh(COD). This complex reacted with excess PPh$\\sb3$, giving the CH$\\sb2$Cl$\\sb2$-soluble species: (PPh$\\sb3)\\sb2$Rh($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Pd($\\mu$-S)$\\sb2$W($\\mu$-S)$\\sb2$Rh(PPh$\\sb3)\\sb2$.","Complexes of general formula (($\\eta\\sp5$-C$\\sb5$H$\\sb4$R)Ru(PPh$\\sb3$)) $\\sb2$ME$\\sb4$ (where R = H, CH$\\sb3$; M = Mo, W; E = S, Se) were synthesized from two equivalents of ($\\eta\\sp5$-C$\\sb5$H$\\sb4$R)Ru(PPh$\\sb3)\\sb2$Cl and one equivalent of the corresponding (Ph$\\sb4$P)$\\sb2$ME$\\sb4$. The WSe$\\sb4$ derivative was prepared using ($t$-BuNH$\\sb3)\\sb2$WSe$\\sb4$, which was obtained from the reaction of W(NH-$t$-Bu)$\\sb2$(N-$t$-Bu)$\\sb2$ with H$\\sb2$Se. These compounds undergo single one electron oxidations in their cyclic voltammograms. Trialkylphosphines, carbon monoxide, and isocyanides (RNC, R = $t$-Bu, Me, and Bz) were found to displace the PPh$\\sb3$ ligands in (CpRu(PPh$\\sb3$)) $\\sb2$WS$\\sb4$ 2. In the case of CO however, substitution was observed to occur at only one ruthenium center. A kinetic study of the substitution of PPh$\\sb3$ by $t$-BuNC in 2 revealed that the rate was independent of ($t$-BuNC), indicating a dissociative mechanism.","A number of (L$\\sb{\\rm n}$M$\\sp\\prime$) $\\sb2$WS$\\sb4$ complexes were prepared from WS$\\sb4\\sp{2-}$ and compounds of the type (L$\\sb{\\rm n}$M($\\mu$-Cl)) $\\sb2$. These included complexes where L$\\sb{\\rm n}$M was (NBD)Rh, (COD)Ir, ($\\eta\\sp5$-C$\\sb5$Me$\\sb5$)RhCl, and (allyl)Pd. The Rh(III) and Pd(II) derivatives were characterized by X-ray crystallography which showed M-W distances of 2.90A(av.) and 2.80A(av.) respectively. Poorly soluble complexes of the type (COD)PtMS$\\sb4$ (M = Mo, W) were prepared from the reaction of (COD)PtCl$\\sb2$ and (Ph$\\sb4$P)$\\sb2$MS$\\sb4$. The thermal gravimetric analyses of ((COD)Rh) $\\sb2$MS$\\sb4$ and (COD)PtMS$\\sb4$ over temperature ranges of 50-900$\\sp\\circ$C indicate the formation of MRh$\\sb2$S$\\sb{\\rm x}$ (x = 2 or 2.5) and PtMS formulas. We suggest that these complexes should be examined as precursors to new ternary metal sulfides. (Abstract shortened with permission of author.)","Made available in DSpace on 2014-12-15T23:19:23Z (GMT). No. of bitstreams: 1 8908710.pdf: 5167483 bytes, checksum: 4533f5c86c2cb6c05a24e6b4786f8837 (MD5) Previous issue date: 1988","Embargo set by: Seth Robbins for item 70590 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","158 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988."],"dc:identifier":["http://hdl.handle.net/2142/70424","(UMI)AAI8908710"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Organometallic and Inorganic Derivatives of the Tetrathiometallates"],"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"}