{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/20157"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/20157","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Zinc polysulfides as precursors to zinc sulfide and as group transfer reagents","abstract":"In the first part of the thesis, reactions of zinc powder with solutions of elemental sulfur in various donor solvents are described. Complexes of the type $\\rm ZnS\\sb6$(N-donor)$\\sb2$ are obtained for the ligands tetramethylethylenediamine (TMEDA), N-methylimidazole (MeIm), and 4-(N,N-dimethylamino)pyridine (DMAP). Ligand competition studies on pyridine solutions revealed that the relative stability constants $\\rm (DMAP>MeIm>TMEDA>pyridine)$ parallels the basicity of the ligands. Crystallographic analysis shows that $\\rm ZnS\\sb6$(TMEDA) adopts a tetrahedral geometry with a seven-membered $\\rm ZnS\\sb6$ ring. Solutions of $\\rm ZnS\\sb6$(TMEDA) undergo ligand exchange with other ligands L to afford $\\rm ZnS\\sb6L\\sb2$ (L = MeIm, quinuclidine). The pyridine analog, $\\rm ZnS\\sb6py\\sb2$ also undergoes ligand substitution with TEEDA $(N,N,N\\prime,N\\prime$-tetraethylethylenediamine) and ($-$)-sparteine to afford $\\rm ZnS\\sb6$(TEEDA) and $\\rm ZnS\\sb6\\{(-)$-sparteine$\\};$ these complexes can not be prepared by the reaction of sulfur and zinc dust in TEEDA or ($-$)-sparteine. Optical and reactivity studies showed that MeIm, but not pyridine, displaces the polysulfide from $\\rm ZnS\\sb6(MeIm)\\sb2$ as indicated by the appearance of the chromophore $\\rm S\\sb3\\sp-.$ ZnS$\\sb6$(TMEDA) reacts with the electrophilic acetylenes methylpropiolate and dimethylacetylenedicarboxylate (DMAD) to give the dithiolene complexes $\\rm ZnS\\sb2C\\sb2R(CO\\sb2Me)$(TMEDA), where R = $\\rm CO\\sb2Me,$ H.","abstract_html":"In the first part of the thesis, reactions of zinc powder with solutions of elemental sulfur in various donor solvents are described. Complexes of the type $\\rm ZnS\\sb6$(N-donor)$\\sb2$ are obtained for the ligands tetramethylethylenediamine (TMEDA), N-methylimidazole (MeIm), and 4-(N,N-dimethylamino)pyridine (DMAP). Ligand competition studies on pyridine solutions revealed that the relative stability constants $\\rm (DMAP>MeIm>TMEDA>pyridine)$ parallels the basicity of the ligands. Crystallographic analysis shows that $\\rm ZnS\\sb6$(TMEDA) adopts a tetrahedral geometry with a seven-membered $\\rm ZnS\\sb6$ ring. Solutions of $\\rm ZnS\\sb6$(TMEDA) undergo ligand exchange with other ligands L to afford $\\rm ZnS\\sb6L\\sb2$ (L = MeIm, quinuclidine). The pyridine analog, $\\rm ZnS\\sb6py\\sb2$ also undergoes ligand substitution with TEEDA $(N,N,N\\prime,N\\prime$-tetraethylethylenediamine) and ($-$)-sparteine to afford $\\rm ZnS\\sb6$(TEEDA) and $\\rm ZnS\\sb6\\{(-)$-sparteine$\\};$ these complexes can not be prepared by the reaction of sulfur and zinc dust in TEEDA or ($-$)-sparteine. Optical and reactivity studies showed that MeIm, but not pyridine, displaces the polysulfide from $\\rm ZnS\\sb6(MeIm)\\sb2$ as indicated by the appearance of the chromophore $\\rm S\\sb3\\sp-.$ ZnS$\\sb6$(TMEDA) reacts with the electrophilic acetylenes methylpropiolate and dimethylacetylenedicarboxylate (DMAD) to give the dithiolene complexes $\\rm ZnS\\sb2C\\sb2R(CO\\sb2Me)$(TMEDA), where R = $\\rm CO\\sb2Me,$ H.","abstract_has_math":true,"creators":["Verma, Atul Kumar"],"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":2011,"date_issued":"2011-05-07T12:30:38Z","date_published":"2011-05-07T12:30:38Z","updated_at":"2026-07-22T22:25:15Z","subjects":["Chemistry, Inorganic","Engineering, Materials Science"],"languages":["eng"],"rights":["Copyright 1996 Verma, Atul Kumar"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591199529","AAI9712470","(UMI)AAI9712470"],"render_values":[{"text":"9780591199529","href":null,"code":true},{"text":"AAI9712470","href":null,"code":true},{"text":"(UMI)AAI9712470","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/20157","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":["Verma, Atul Kumar"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:30:38Z","10000-01-01","1996"]},{"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","Engineering, Materials Science"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1996 Verma, Atul Kumar"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591199529","AAI9712470","(UMI)AAI9712470","http://hdl.handle.net/2142/20157"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["In the first part of the thesis, reactions of zinc powder with solutions of elemental sulfur in various donor solvents are described. Complexes of the type $\\rm ZnS\\sb6$(N-donor)$\\sb2$ are obtained for the ligands tetramethylethylenediamine (TMEDA), N-methylimidazole (MeIm), and 4-(N,N-dimethylamino)pyridine (DMAP). Ligand competition studies on pyridine solutions revealed that the relative stability constants $\\rm (DMAP>MeIm>TMEDA>pyridine)$ parallels the basicity of the ligands. Crystallographic analysis shows that $\\rm ZnS\\sb6$(TMEDA) adopts a tetrahedral geometry with a seven-membered $\\rm ZnS\\sb6$ ring. Solutions of $\\rm ZnS\\sb6$(TMEDA) undergo ligand exchange with other ligands L to afford $\\rm ZnS\\sb6L\\sb2$ (L = MeIm, quinuclidine). The pyridine analog, $\\rm ZnS\\sb6py\\sb2$ also undergoes ligand substitution with TEEDA $(N,N,N\\prime,N\\prime$-tetraethylethylenediamine) and ($-$)-sparteine to afford $\\rm ZnS\\sb6$(TEEDA) and $\\rm ZnS\\sb6\\{(-)$-sparteine$\\};$ these complexes can not be prepared by the reaction of sulfur and zinc dust in TEEDA or ($-$)-sparteine. Optical and reactivity studies showed that MeIm, but not pyridine, displaces the polysulfide from $\\rm ZnS\\sb6(MeIm)\\sb2$ as indicated by the appearance of the chromophore $\\rm S\\sb3\\sp-.$ ZnS$\\sb6$(TMEDA) reacts with the electrophilic acetylenes methylpropiolate and dimethylacetylenedicarboxylate (DMAD) to give the dithiolene complexes $\\rm ZnS\\sb2C\\sb2R(CO\\sb2Me)$(TMEDA), where R = $\\rm CO\\sb2Me,$ H.","The second portion of thesis studies the conversion of $\\rm ZnS\\sb6$(N-donor)$\\sb2$ complexes into ZnS and related materials. Solid $\\rm ZnS\\sb6(TMEDA)$ cleanly decomposes at $350\\sp\\circ$C to cubic ZnS, as indicated by TGA and preparative scale studies. Submicron cubic ZnS is generated upon partial desulfurization of $\\rm ZnS\\sb6(TMEDA)$ with tertiary phosphines as established by electron microscopic studies. The reaction of $\\rm ZnS\\sb6(MeIm)\\sb2$ with 5 equiv of zinc dust affords nanosize insoluble material $\\rm ZnS(MeIm)\\sb{1\\sim x}\\ (x\\approx 0{-}0.3).$ This unusual species, unlike cubic ZnS, is very reactive towards MeIm solutions of sulfur and affords $\\rm ZnS\\sb6(MeIm)\\sb2.$ The TGA, XPS, CL, and SS MAS $\\sp{13}$C NMR spectroscopic measurements suggest a strong Zn-MeIm interaction in $\\rm ZnS(MeIm)\\sb{1\\sim x}.$ This species also reacts with $\\rm Cu\\sb4S\\sb{10}(MeIm)\\sb4$ to afford $\\rm\\lbrack Zn(MeIm)\\sb6\\rbrack\\lbrack Cu\\sb4S\\sb{12}\\rbrack.$","In the final Chapter, the species $\\rm ZnS\\sb6(TMEDA)$ has been developed as a potent polysulfido-transfer reagent. The reaction of this zinc reagent with $\\rm Cp\\sb2TiCl\\sb2$ gives $\\rm Cp\\sb2TiS\\sb5.$ When a $\\rm CS\\sb2$ slurry of $\\rm ZnS\\sb6(TMEDA)$ is treated with $\\rm Se\\sb2Cl\\sb2,$ chalcogenospecific formation of 1,2-$\\rm Se\\sb2S\\sb6$ is observed, as confirmed by reverse phase HPLC, Raman, and $\\sp{77}$Se NMR spectroscopic measurements. A $\\rm CS\\sb2$ solution of 1,2-$\\rm Se\\sb2S\\sb6$ is mildly reactive towards UV-photolysis, rearranging to its 1,3-, 1,4-, 1,5-, and other isomers over the course of several hours. The reaction of $\\rm CH\\sb2Cl\\sb2$ solutions of $\\rm ZnS\\sb6(TMEDA)$ with $\\rm TiCl\\sb4$ affords a brown solid $\\rm TiS\\sb{x}.$ Extraction of $\\rm TiS\\sb{x}$ with MeIm, affords an air-sensitive molecular complex $\\rm Ti(S\\sb2)\\sb2(MeIm)\\sb3.$ The crystal structure reveals a pseudo trigonal-bipyramidal geometry around Ti, with the two MeIm ligands bound axially. The oxidation of $\\rm TiS\\sb4(MeIm)\\sb3$ generates a dinuclear $\\mu$-oxo species $\\rm\\lbrack Ti\\sb2(S\\sb2)\\sb2(\\mu$-$\\rm S\\sb2)(\\mu$-O)$\\rm (MeIm)\\sb4\\rbrack ,$ as confirmed by single crystal X-ray crystallography.","Made available in DSpace on 2011-05-07T12:30:38Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712470.pdf: 6252156 bytes, checksum: 742dea4ec25b06a99ff1784d1df2ed06 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:41:57Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:13-05:00 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":["Zinc polysulfides as precursors to zinc sulfide and as group transfer reagents"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Verma, Atul Kumar"],"dc:date":["2011-05-07T12:30:38Z","10000-01-01","1996"],"dc:description":["In the first part of the thesis, reactions of zinc powder with solutions of elemental sulfur in various donor solvents are described. Complexes of the type $\\rm ZnS\\sb6$(N-donor)$\\sb2$ are obtained for the ligands tetramethylethylenediamine (TMEDA), N-methylimidazole (MeIm), and 4-(N,N-dimethylamino)pyridine (DMAP). Ligand competition studies on pyridine solutions revealed that the relative stability constants $\\rm (DMAP>MeIm>TMEDA>pyridine)$ parallels the basicity of the ligands. Crystallographic analysis shows that $\\rm ZnS\\sb6$(TMEDA) adopts a tetrahedral geometry with a seven-membered $\\rm ZnS\\sb6$ ring. Solutions of $\\rm ZnS\\sb6$(TMEDA) undergo ligand exchange with other ligands L to afford $\\rm ZnS\\sb6L\\sb2$ (L = MeIm, quinuclidine). The pyridine analog, $\\rm ZnS\\sb6py\\sb2$ also undergoes ligand substitution with TEEDA $(N,N,N\\prime,N\\prime$-tetraethylethylenediamine) and ($-$)-sparteine to afford $\\rm ZnS\\sb6$(TEEDA) and $\\rm ZnS\\sb6\\{(-)$-sparteine$\\};$ these complexes can not be prepared by the reaction of sulfur and zinc dust in TEEDA or ($-$)-sparteine. Optical and reactivity studies showed that MeIm, but not pyridine, displaces the polysulfide from $\\rm ZnS\\sb6(MeIm)\\sb2$ as indicated by the appearance of the chromophore $\\rm S\\sb3\\sp-.$ ZnS$\\sb6$(TMEDA) reacts with the electrophilic acetylenes methylpropiolate and dimethylacetylenedicarboxylate (DMAD) to give the dithiolene complexes $\\rm ZnS\\sb2C\\sb2R(CO\\sb2Me)$(TMEDA), where R = $\\rm CO\\sb2Me,$ H.","The second portion of thesis studies the conversion of $\\rm ZnS\\sb6$(N-donor)$\\sb2$ complexes into ZnS and related materials. Solid $\\rm ZnS\\sb6(TMEDA)$ cleanly decomposes at $350\\sp\\circ$C to cubic ZnS, as indicated by TGA and preparative scale studies. Submicron cubic ZnS is generated upon partial desulfurization of $\\rm ZnS\\sb6(TMEDA)$ with tertiary phosphines as established by electron microscopic studies. The reaction of $\\rm ZnS\\sb6(MeIm)\\sb2$ with 5 equiv of zinc dust affords nanosize insoluble material $\\rm ZnS(MeIm)\\sb{1\\sim x}\\ (x\\approx 0{-}0.3).$ This unusual species, unlike cubic ZnS, is very reactive towards MeIm solutions of sulfur and affords $\\rm ZnS\\sb6(MeIm)\\sb2.$ The TGA, XPS, CL, and SS MAS $\\sp{13}$C NMR spectroscopic measurements suggest a strong Zn-MeIm interaction in $\\rm ZnS(MeIm)\\sb{1\\sim x}.$ This species also reacts with $\\rm Cu\\sb4S\\sb{10}(MeIm)\\sb4$ to afford $\\rm\\lbrack Zn(MeIm)\\sb6\\rbrack\\lbrack Cu\\sb4S\\sb{12}\\rbrack.$","In the final Chapter, the species $\\rm ZnS\\sb6(TMEDA)$ has been developed as a potent polysulfido-transfer reagent. The reaction of this zinc reagent with $\\rm Cp\\sb2TiCl\\sb2$ gives $\\rm Cp\\sb2TiS\\sb5.$ When a $\\rm CS\\sb2$ slurry of $\\rm ZnS\\sb6(TMEDA)$ is treated with $\\rm Se\\sb2Cl\\sb2,$ chalcogenospecific formation of 1,2-$\\rm Se\\sb2S\\sb6$ is observed, as confirmed by reverse phase HPLC, Raman, and $\\sp{77}$Se NMR spectroscopic measurements. A $\\rm CS\\sb2$ solution of 1,2-$\\rm Se\\sb2S\\sb6$ is mildly reactive towards UV-photolysis, rearranging to its 1,3-, 1,4-, 1,5-, and other isomers over the course of several hours. The reaction of $\\rm CH\\sb2Cl\\sb2$ solutions of $\\rm ZnS\\sb6(TMEDA)$ with $\\rm TiCl\\sb4$ affords a brown solid $\\rm TiS\\sb{x}.$ Extraction of $\\rm TiS\\sb{x}$ with MeIm, affords an air-sensitive molecular complex $\\rm Ti(S\\sb2)\\sb2(MeIm)\\sb3.$ The crystal structure reveals a pseudo trigonal-bipyramidal geometry around Ti, with the two MeIm ligands bound axially. The oxidation of $\\rm TiS\\sb4(MeIm)\\sb3$ generates a dinuclear $\\mu$-oxo species $\\rm\\lbrack Ti\\sb2(S\\sb2)\\sb2(\\mu$-$\\rm S\\sb2)(\\mu$-O)$\\rm (MeIm)\\sb4\\rbrack ,$ as confirmed by single crystal X-ray crystallography.","Made available in DSpace on 2011-05-07T12:30:38Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712470.pdf: 6252156 bytes, checksum: 742dea4ec25b06a99ff1784d1df2ed06 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:41:57Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:13-05:00 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":["9780591199529","AAI9712470","(UMI)AAI9712470","http://hdl.handle.net/2142/20157"],"dc:language":["eng"],"dc:rights":["Copyright 1996 Verma, Atul Kumar"],"dc:subject":["Chemistry, Inorganic","Engineering, Materials Science"],"dc:title":["Zinc polysulfides as precursors to zinc sulfide and as group transfer reagents"],"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":"2026-07-22T22:25:15Z"}