{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70405"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70405","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis, Characterization, and Reactivity of Alkylphosphomolybdates: Oxidation, Dehydration, and Isomerization","abstract":"The alkyl and silyl phosphomolybdates (P$\\sb3$O$\\sb9$)MoO$\\sb2$OR((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ $\\{$R = CH$\\sb3$, CH$\\sb2$CH$\\sb3$, 1, CH(CH$\\sb3)\\sb2$, CH$\\sb2$CH=CH$\\sb2$, CH$\\sb2$CH$\\sb2$C$\\sb6$H$\\sb5$, and Si(CH$\\sb3)\\sb3\\}$ have been prepared and characterized. A single crystal X-ray diffraction study reveals that in 1, the P$\\sb3$O$\\sb9\\sp{3-}$ ligand acts as a tridentate ligand coordinated to MoO$\\sb2$OCH$\\sb2$CH$\\sb3\\sp+$ unit. Two short intramolecular CH$\\cdots$OMo contacts between the methylene hydrogens and the oxygens of P-O and Mo=O are found in anion 1. Based on $\\sp{31}$P, $\\sp $O, and $\\sp1$H NMR studies, hydrolysis of (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH$\\sb3\\sp{2-}$ produces the anhydride ((P$\\sb3$O$\\sb9$)MoO$\\sb2$) $\\sb2$O$\\sp{4-}$ and the acid (P$\\sb3$O$\\sb9$)MoO$\\sb3$H$\\sp{2-}$. In the presence of excess methanol, the methyl ester (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH$\\sb3\\sp{2-}$ can be regenerated from the anhydride and the acid. The acid slowly dimerizes to form the dimer, (P$\\sb3$O$\\sb $HMoO$\\sb2)\\sb2\\sp{4-}$, which has been isolated in crystalline form. An X-ray crystal structural analysis of this dimer reveals the presence of a tetradentate linear triphosphate ligand. The hydrogens in this anion were located by $\\sp{31}$P NMR study.","abstract_html":"The alkyl and silyl phosphomolybdates (P$\\sb3$O$\\sb9$)MoO$\\sb2$OR((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ $\\{$R = CH$\\sb3$, CH$\\sb2$CH$\\sb3$, 1, CH(CH$\\sb3)\\sb2$, CH$\\sb2$CH=CH$\\sb2$, CH$\\sb2$CH$\\sb2$C$\\sb6$H$\\sb5$, and Si(CH$\\sb3)\\sb3\\}$ have been prepared and characterized. A single crystal X-ray diffraction study reveals that in 1, the P$\\sb3$O$\\sb9\\sp{3-}$ ligand acts as a tridentate ligand coordinated to MoO$\\sb2$OCH$\\sb2$CH$\\sb3\\sp+$ unit. Two short intramolecular CH$\\cdots$OMo contacts between the methylene hydrogens and the oxygens of P-O and Mo=O are found in anion 1. Based on $\\sp{31}$P, $\\sp $O, and $\\sp1$H NMR studies, hydrolysis of (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH$\\sb3\\sp{2-}$ produces the anhydride ((P$\\sb3$O$\\sb9$)MoO$\\sb2$) $\\sb2$O$\\sp{4-}$ and the acid (P$\\sb3$O$\\sb9$)MoO$\\sb3$H$\\sp{2-}$. In the presence of excess methanol, the methyl ester (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH$\\sb3\\sp{2-}$ can be regenerated from the anhydride and the acid. The acid slowly dimerizes to form the dimer, (P$\\sb3$O$\\sb $HMoO$\\sb2)\\sb2\\sp{4-}$, which has been isolated in crystalline form. An X-ray crystal structural analysis of this dimer reveals the presence of a tetradentate linear triphosphate ligand. The hydrogens in this anion were located by $\\sp{31}$P NMR study.","abstract_has_math":true,"creators":["Wang, Ren-Chain"],"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":2014,"date_issued":"2014-12-15T23:19:13Z","date_published":"2014-12-15T23:19:13Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8815439"],"render_values":[{"text":"(UMI)AAI8815439","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70405","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":["Wang, Ren-Chain"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:19:13Z","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/2142/70405","(UMI)AAI8815439"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The alkyl and silyl phosphomolybdates (P$\\sb3$O$\\sb9$)MoO$\\sb2$OR((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ $\\{$R = CH$\\sb3$, CH$\\sb2$CH$\\sb3$, 1, CH(CH$\\sb3)\\sb2$, CH$\\sb2$CH=CH$\\sb2$, CH$\\sb2$CH$\\sb2$C$\\sb6$H$\\sb5$, and Si(CH$\\sb3)\\sb3\\}$ have been prepared and characterized. A single crystal X-ray diffraction study reveals that in 1, the P$\\sb3$O$\\sb9\\sp{3-}$ ligand acts as a tridentate ligand coordinated to MoO$\\sb2$OCH$\\sb2$CH$\\sb3\\sp+$ unit. Two short intramolecular CH$\\cdots$OMo contacts between the methylene hydrogens and the oxygens of P-O and Mo=O are found in anion 1. Based on $\\sp{31}$P, $\\sp $O, and $\\sp1$H NMR studies, hydrolysis of (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH$\\sb3\\sp{2-}$ produces the anhydride ((P$\\sb3$O$\\sb9$)MoO$\\sb2$) $\\sb2$O$\\sp{4-}$ and the acid (P$\\sb3$O$\\sb9$)MoO$\\sb3$H$\\sp{2-}$. In the presence of excess methanol, the methyl ester (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH$\\sb3\\sp{2-}$ can be regenerated from the anhydride and the acid. The acid slowly dimerizes to form the dimer, (P$\\sb3$O$\\sb $HMoO$\\sb2)\\sb2\\sp{4-}$, which has been isolated in crystalline form. An X-ray crystal structural analysis of this dimer reveals the presence of a tetradentate linear triphosphate ligand. The hydrogens in this anion were located by $\\sp{31}$P NMR study.","Thermolysis of (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH$\\sb2$CH$\\sb3$((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$, 1, in CH$\\sb3$CN produces acetaldehyde, ethanol, and unidentified soluble inorganic products. According to deuterium labeling experiments, the rate-determining step of the reaction is the methylene C-H cleavage. An intramolecular mechanism is proposed based on these kinetic data and the short CH$\\cdots$OMo contact found in the structure. Photolysis of 1 gives ethylene, acetaldehyde, ethanol, and unidentified soluble inorganic products. A deuterium labeling experiment revealed that the cleavage of methylene C-H bond and methyl C-H bond are the rate-determining steps for acetaldehyde and ethylene formation, respectively. Intramolecular mechanisms which are analogous to the well-known organic Norrish Type II reaction have been proposed for these photoreactions.","The allyl ester (P$\\sb3$O$\\sb9)$MoO$\\sb2$OCH$\\sb2$CH=CH$\\sb2$((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ isomerizes in CH$\\sb3$CN at 80$\\sp\\circ$C to form the enol ester cis-(P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH=CHCH$\\sb3$((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$. Under the same reaction conditions, allyl-1,1-d$\\sb2$ ester (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCD$\\sb2$CH=CH$\\sb2$((n- C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ isomerizes to yield enol-1,3-d$\\sb2$ ester cis-(P$\\sb3$O$\\sb9$)MoO$\\sb2$OCD=CHCH$\\sb2$D((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$. The isomerization kinetics for both allyl esters are first order. The rate-determining step in the isomerization is cleavage of the methylene C-H bond according to the deuterium labeling experiments. Deuterium labeling crossover experiments indicate the isomerization is intramolecular. A mechanism is proposed for this isomerization that involves a 1,3 proton shift via an intermediate in which the proton is bonded to a molybdenyl (Mo=O) oxygen.","Made available in DSpace on 2014-12-15T23:19:13Z (GMT). No. of bitstreams: 1 8815439.pdf: 3313896 bytes, checksum: 62e205ec570a67c3385228c75dfb1439 (MD5) Previous issue date: 1988","Embargo set by: Seth Robbins for item 70571 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","133 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988."]},{"key":"dc:title","label":"Title","values":["Synthesis, Characterization, and Reactivity of Alkylphosphomolybdates: Oxidation, Dehydration, and Isomerization"]}]}],"canonical_facts":{"dc:contributor":["Klemperer, Walter G."],"dc:creator":["Wang, Ren-Chain"],"dc:date":["2014-12-15T23:19:13Z","10000-01-01","1988"],"dc:description":["The alkyl and silyl phosphomolybdates (P$\\sb3$O$\\sb9$)MoO$\\sb2$OR((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ $\\{$R = CH$\\sb3$, CH$\\sb2$CH$\\sb3$, 1, CH(CH$\\sb3)\\sb2$, CH$\\sb2$CH=CH$\\sb2$, CH$\\sb2$CH$\\sb2$C$\\sb6$H$\\sb5$, and Si(CH$\\sb3)\\sb3\\}$ have been prepared and characterized. A single crystal X-ray diffraction study reveals that in 1, the P$\\sb3$O$\\sb9\\sp{3-}$ ligand acts as a tridentate ligand coordinated to MoO$\\sb2$OCH$\\sb2$CH$\\sb3\\sp+$ unit. Two short intramolecular CH$\\cdots$OMo contacts between the methylene hydrogens and the oxygens of P-O and Mo=O are found in anion 1. Based on $\\sp{31}$P, $\\sp $O, and $\\sp1$H NMR studies, hydrolysis of (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH$\\sb3\\sp{2-}$ produces the anhydride ((P$\\sb3$O$\\sb9$)MoO$\\sb2$) $\\sb2$O$\\sp{4-}$ and the acid (P$\\sb3$O$\\sb9$)MoO$\\sb3$H$\\sp{2-}$. In the presence of excess methanol, the methyl ester (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH$\\sb3\\sp{2-}$ can be regenerated from the anhydride and the acid. The acid slowly dimerizes to form the dimer, (P$\\sb3$O$\\sb $HMoO$\\sb2)\\sb2\\sp{4-}$, which has been isolated in crystalline form. An X-ray crystal structural analysis of this dimer reveals the presence of a tetradentate linear triphosphate ligand. The hydrogens in this anion were located by $\\sp{31}$P NMR study.","Thermolysis of (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH$\\sb2$CH$\\sb3$((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$, 1, in CH$\\sb3$CN produces acetaldehyde, ethanol, and unidentified soluble inorganic products. According to deuterium labeling experiments, the rate-determining step of the reaction is the methylene C-H cleavage. An intramolecular mechanism is proposed based on these kinetic data and the short CH$\\cdots$OMo contact found in the structure. Photolysis of 1 gives ethylene, acetaldehyde, ethanol, and unidentified soluble inorganic products. A deuterium labeling experiment revealed that the cleavage of methylene C-H bond and methyl C-H bond are the rate-determining steps for acetaldehyde and ethylene formation, respectively. Intramolecular mechanisms which are analogous to the well-known organic Norrish Type II reaction have been proposed for these photoreactions.","The allyl ester (P$\\sb3$O$\\sb9)$MoO$\\sb2$OCH$\\sb2$CH=CH$\\sb2$((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ isomerizes in CH$\\sb3$CN at 80$\\sp\\circ$C to form the enol ester cis-(P$\\sb3$O$\\sb9$)MoO$\\sb2$OCH=CHCH$\\sb3$((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$. Under the same reaction conditions, allyl-1,1-d$\\sb2$ ester (P$\\sb3$O$\\sb9$)MoO$\\sb2$OCD$\\sb2$CH=CH$\\sb2$((n- C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$ isomerizes to yield enol-1,3-d$\\sb2$ ester cis-(P$\\sb3$O$\\sb9$)MoO$\\sb2$OCD=CHCH$\\sb2$D((n-C$\\sb4$H$\\sb9)\\sb4$N) $\\sb2$. The isomerization kinetics for both allyl esters are first order. The rate-determining step in the isomerization is cleavage of the methylene C-H bond according to the deuterium labeling experiments. Deuterium labeling crossover experiments indicate the isomerization is intramolecular. A mechanism is proposed for this isomerization that involves a 1,3 proton shift via an intermediate in which the proton is bonded to a molybdenyl (Mo=O) oxygen.","Made available in DSpace on 2014-12-15T23:19:13Z (GMT). No. of bitstreams: 1 8815439.pdf: 3313896 bytes, checksum: 62e205ec570a67c3385228c75dfb1439 (MD5) Previous issue date: 1988","Embargo set by: Seth Robbins for item 70571 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","133 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988."],"dc:identifier":["http://hdl.handle.net/2142/70405","(UMI)AAI8815439"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Synthesis, Characterization, and Reactivity of Alkylphosphomolybdates: Oxidation, Dehydration, and Isomerization"],"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"}