{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/20991"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/20991","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis, structure, and reactivity of polyoxovanadates in nonaqueous media","abstract":"Exploration of the nonaqueous chemistry of polyoxovanadates was initiated by studying the following reaction: x $\\rm H\\sb3V\\sb{10}O\\sb{28}\\sp{3-}$ + y OH$\\sp-$ $\\to$ 10 $\\rm H\\sb nV\\sb xO\\sb m\\sp{z-}$ + (y-n) H$\\sb2$O involving the addition of (TBA)(OH) to ($\\rm H\\sb3V\\sb{10}O\\sb{28}$)(TBA)$\\sb3$ in CH$\\sb3$CN, where TBA = tetra-n-butylammonium. This resulted in the synthesis and characterization of two types of soluble species: first, reactive isopolyvanadate species which can serve as good starting materials for the development of the synthetic chemistry of covalent polyoxovanadate derivatives; second, species which have structural features normally associated with those present on solid vanadium oxide surfaces. The first species isolated from this reaction was $\\rm H\\sb2V\\sb{10}O\\sb{28}\\sp{4-}$ as a TBA salt, structural characterization in the solid and solution state reveal that the protonation sites are two OV$\\sb2$ oxygens. This anion was found to be unstable in acetonitrile with respect to disproportionation forming two new polyoxovanadates, $\\rm V\\sb5O\\sb{14}\\sp{3-}$ and $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$.","abstract_html":"Exploration of the nonaqueous chemistry of polyoxovanadates was initiated by studying the following reaction: x $\\rm H\\sb3V\\sb{10}O\\sb{28}\\sp{3-}$ + y OH$\\sp-$ $\\to$ 10 $\\rm H\\sb nV\\sb xO\\sb m\\sp{z-}$ + (y-n) H$\\sb2$O involving the addition of (TBA)(OH) to ($\\rm H\\sb3V\\sb{10}O\\sb{28}$)(TBA)$\\sb3$ in CH$\\sb3$CN, where TBA = tetra-n-butylammonium. This resulted in the synthesis and characterization of two types of soluble species: first, reactive isopolyvanadate species which can serve as good starting materials for the development of the synthetic chemistry of covalent polyoxovanadate derivatives; second, species which have structural features normally associated with those present on solid vanadium oxide surfaces. The first species isolated from this reaction was $\\rm H\\sb2V\\sb{10}O\\sb{28}\\sp{4-}$ as a TBA salt, structural characterization in the solid and solution state reveal that the protonation sites are two OV$\\sb2$ oxygens. This anion was found to be unstable in acetonitrile with respect to disproportionation forming two new polyoxovanadates, $\\rm V\\sb5O\\sb{14}\\sp{3-}$ and $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$.","abstract_has_math":true,"creators":["Yaghi, Omar M."],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Klemperer, Walter G."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T12:55:09Z","date_published":"2011-05-07T12:55:09Z","updated_at":"2026-07-22T22:25:17Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1990 Yaghi, Omar M."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9114471","(UMI)AAI9114471"],"render_values":[{"text":"AAI9114471","href":null,"code":true},{"text":"(UMI)AAI9114471","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/20991","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Klemperer, Walter G."]},{"key":"dc:creator","label":"Author","values":["Yaghi, Omar M."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:55:09Z","10000-01-01","1990"]},{"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":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1990 Yaghi, Omar M."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9114471","(UMI)AAI9114471","http://hdl.handle.net/2142/20991"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Exploration of the nonaqueous chemistry of polyoxovanadates was initiated by studying the following reaction: x $\\rm H\\sb3V\\sb{10}O\\sb{28}\\sp{3-}$ + y OH$\\sp-$ $\\to$ 10 $\\rm H\\sb nV\\sb xO\\sb m\\sp{z-}$ + (y-n) H$\\sb2$O involving the addition of (TBA)(OH) to ($\\rm H\\sb3V\\sb{10}O\\sb{28}$)(TBA)$\\sb3$ in CH$\\sb3$CN, where TBA = tetra-n-butylammonium. This resulted in the synthesis and characterization of two types of soluble species: first, reactive isopolyvanadate species which can serve as good starting materials for the development of the synthetic chemistry of covalent polyoxovanadate derivatives; second, species which have structural features normally associated with those present on solid vanadium oxide surfaces. The first species isolated from this reaction was $\\rm H\\sb2V\\sb{10}O\\sb{28}\\sp{4-}$ as a TBA salt, structural characterization in the solid and solution state reveal that the protonation sites are two OV$\\sb2$ oxygens. This anion was found to be unstable in acetonitrile with respect to disproportionation forming two new polyoxovanadates, $\\rm V\\sb5O\\sb{14}\\sp{3-}$ and $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$.","The $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ anion is formed as an acetonitrile inclusion complex, $\\rm CH\\sb3CN\\subset(V\\sb{12}O\\sb{32}\\sp{4-}$). The nido-$\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ cage framework is a new structure type and can be derived from two different types of closo-cage frameworks. The vanadium coordination geometry within the $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ cage is similar to that observed in square-pyramidal vanadium(V) compounds such as orthorhombic $\\rm V\\sb2O\\sb5$ and $\\alpha$-VOPO$\\sb4$.","The $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ is the first molecular inorganic species known to form inclusion complexes in solution. Synthesis and structural characterization of the $\\rm CH\\sb3NO\\sb2$, $\\rm C\\sb6H\\sb5NO\\sb2$, p-$\\rm CH\\sb3C\\sb6H\\sb4CN$, $\\rm C\\sb6H\\sb5CN$, $\\rm NCCH\\sb2CH\\sb2CN$ and 1,2-$\\rm CH\\sb2CH\\sb2Cl\\sb2$ host-guest complexes has been achieved. The equilibrium constants for host-guest complexation have been derived, and in some cases the enthalpy and entropy of binding have been established quantitatively.","The structural analogy between orthorhombic $\\rm V\\sb2O\\sb5$ layers and $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ host molecules, raises the possibility that this host framework might be capable of affecting C-H activation. Coordinatively unsaturated vanadium sites in vanadates such as $\\rm (VO)\\sb2P\\sb2O\\sb7$ can react with $\\rm CH\\sb3CN$ molecules. The remaining question is whether $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ can react with saturated hydrocarbons. (Abstract shortened with permission of author.)","Made available in DSpace on 2011-05-07T12:55:09Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9114471.pdf: 3771205 bytes, checksum: 69197fcacb6f9e71ba008863a6e3497a (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:47:44Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:21:34-05:00 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":["Synthesis, structure, and reactivity of polyoxovanadates in nonaqueous media"]}]}],"canonical_facts":{"dc:contributor":["Klemperer, Walter G."],"dc:creator":["Yaghi, Omar M."],"dc:date":["2011-05-07T12:55:09Z","10000-01-01","1990"],"dc:description":["Exploration of the nonaqueous chemistry of polyoxovanadates was initiated by studying the following reaction: x $\\rm H\\sb3V\\sb{10}O\\sb{28}\\sp{3-}$ + y OH$\\sp-$ $\\to$ 10 $\\rm H\\sb nV\\sb xO\\sb m\\sp{z-}$ + (y-n) H$\\sb2$O involving the addition of (TBA)(OH) to ($\\rm H\\sb3V\\sb{10}O\\sb{28}$)(TBA)$\\sb3$ in CH$\\sb3$CN, where TBA = tetra-n-butylammonium. This resulted in the synthesis and characterization of two types of soluble species: first, reactive isopolyvanadate species which can serve as good starting materials for the development of the synthetic chemistry of covalent polyoxovanadate derivatives; second, species which have structural features normally associated with those present on solid vanadium oxide surfaces. The first species isolated from this reaction was $\\rm H\\sb2V\\sb{10}O\\sb{28}\\sp{4-}$ as a TBA salt, structural characterization in the solid and solution state reveal that the protonation sites are two OV$\\sb2$ oxygens. This anion was found to be unstable in acetonitrile with respect to disproportionation forming two new polyoxovanadates, $\\rm V\\sb5O\\sb{14}\\sp{3-}$ and $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$.","The $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ anion is formed as an acetonitrile inclusion complex, $\\rm CH\\sb3CN\\subset(V\\sb{12}O\\sb{32}\\sp{4-}$). The nido-$\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ cage framework is a new structure type and can be derived from two different types of closo-cage frameworks. The vanadium coordination geometry within the $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ cage is similar to that observed in square-pyramidal vanadium(V) compounds such as orthorhombic $\\rm V\\sb2O\\sb5$ and $\\alpha$-VOPO$\\sb4$.","The $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ is the first molecular inorganic species known to form inclusion complexes in solution. Synthesis and structural characterization of the $\\rm CH\\sb3NO\\sb2$, $\\rm C\\sb6H\\sb5NO\\sb2$, p-$\\rm CH\\sb3C\\sb6H\\sb4CN$, $\\rm C\\sb6H\\sb5CN$, $\\rm NCCH\\sb2CH\\sb2CN$ and 1,2-$\\rm CH\\sb2CH\\sb2Cl\\sb2$ host-guest complexes has been achieved. The equilibrium constants for host-guest complexation have been derived, and in some cases the enthalpy and entropy of binding have been established quantitatively.","The structural analogy between orthorhombic $\\rm V\\sb2O\\sb5$ layers and $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ host molecules, raises the possibility that this host framework might be capable of affecting C-H activation. Coordinatively unsaturated vanadium sites in vanadates such as $\\rm (VO)\\sb2P\\sb2O\\sb7$ can react with $\\rm CH\\sb3CN$ molecules. The remaining question is whether $\\rm V\\sb{12}O\\sb{32}\\sp{4-}$ can react with saturated hydrocarbons. (Abstract shortened with permission of author.)","Made available in DSpace on 2011-05-07T12:55:09Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9114471.pdf: 3771205 bytes, checksum: 69197fcacb6f9e71ba008863a6e3497a (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:47:44Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:21:34-05:00 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":["AAI9114471","(UMI)AAI9114471","http://hdl.handle.net/2142/20991"],"dc:language":["eng"],"dc:rights":["Copyright 1990 Yaghi, Omar M."],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Synthesis, structure, and reactivity of polyoxovanadates in nonaqueous media"],"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":"2026-07-22T22:25:17Z"}