{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/19753"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/19753","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Low-nuclearity titanium alkoxides and their rhodium derivatives","abstract":"The reaction of Ti(OPri)4 with 0.078 equiv. of 10 atom% 17O enriched water and 0.6 equiv. of MeOH in i-PrOH solution gave [Ti3O](OPr i)9(OMe) (1). A single crystal X-ray diffraction study of this material indicated that 1 contains two crystallographically-independent Ti3(mu3-O)(mu3-OMe)(mu2-OPr i)3(OPri)6 molecules. The analogous molecule [Ti3O[(OPri)10 (1a) was generated in solution by hydrolysis of Ti(OPri)4 with 0.02 equiv. of water in i-PrOH, and identified using 17O, 13C{1H}, and 1H NMR techniques. Variable temperature NMR spectroscopic studies show that 1 retains its solid state structure at low temperature. It decomposes quickly at room temperature, however, to form Ti(OMe)x(OPr i)4-x, and other polyoxotitanates. 1 has the lowest stability toward parent alcohol and inert hydrocarbon solvents among all known titanium polyoxoalkoxides.","abstract_html":"The reaction of Ti(OPri)4 with 0.078 equiv. of 10 atom% 17O enriched water and 0.6 equiv. of MeOH in i-PrOH solution gave [Ti3O](OPr i)9(OMe) (1). A single crystal X-ray diffraction study of this material indicated that 1 contains two crystallographically-independent Ti3(mu3-O)(mu3-OMe)(mu2-OPr i)3(OPri)6 molecules. The analogous molecule [Ti3O[(OPri)10 (1a) was generated in solution by hydrolysis of Ti(OPri)4 with 0.02 equiv. of water in i-PrOH, and identified using 17O, 13C{1H}, and 1H NMR techniques. Variable temperature NMR spectroscopic studies show that 1 retains its solid state structure at low temperature. It decomposes quickly at room temperature, however, to form Ti(OMe)x(OPr i)4-x, and other polyoxotitanates. 1 has the lowest stability toward parent alcohol and inert hydrocarbon solvents among all known titanium polyoxoalkoxides.","abstract_has_math":false,"creators":["Hao, Jinling"],"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":"2011-05-07T12:17:27Z","date_published":"2011-05-07T12:17:27Z","updated_at":"2026-07-22T22:25:14Z","subjects":["Chemistry, Inorganic","Chemistry, Physical"],"languages":["eng"],"rights":["Copyright 1994 Hao, Jinling"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9503209","(UMI)AAI9503209"],"render_values":[{"text":"AAI9503209","href":null,"code":true},{"text":"(UMI)AAI9503209","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/19753","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":["Hao, Jinling"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:17:27Z","10000-01-01","1994"]},{"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","Chemistry, Physical"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1994 Hao, Jinling"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9503209","(UMI)AAI9503209","http://hdl.handle.net/2142/19753"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The reaction of Ti(OPri)4 with 0.078 equiv. of 10 atom% 17O enriched water and 0.6 equiv. of MeOH in i-PrOH solution gave [Ti3O](OPr i)9(OMe) (1). A single crystal X-ray diffraction study of this material indicated that 1 contains two crystallographically-independent Ti3(mu3-O)(mu3-OMe)(mu2-OPr i)3(OPri)6 molecules. The analogous molecule [Ti3O[(OPri)10 (1a) was generated in solution by hydrolysis of Ti(OPri)4 with 0.02 equiv. of water in i-PrOH, and identified using 17O, 13C{1H}, and 1H NMR techniques. Variable temperature NMR spectroscopic studies show that 1 retains its solid state structure at low temperature. It decomposes quickly at room temperature, however, to form Ti(OMe)x(OPr i)4-x, and other polyoxotitanates. 1 has the lowest stability toward parent alcohol and inert hydrocarbon solvents among all known titanium polyoxoalkoxides.","The reaction of [Rh(COD)(OH)]2 with 3 equiv. of Ti(OPr n)4 affords [Rh(COD)]2Ti(OPrn) 6 (2). An X-ray diffraction study indicates that 2 adopts a butterfly structure with two Rh(COD) acting as wings. In solution, 2 exists in equilibrium with [Rh(COD)(OPrn)] 2 (2a), and Ti(OPrn)4. 2a can also be prepared from the reaction of [Rh(COD)(OH)]2 with one equiv. of Ti(OPrn)4.","The reaction of Ti(OMe)4 with 0.63 equiv. of [C6H 5CH2N(CH3)3]OCH3 in toluene/methanol gave analytically-pure [C6H5CH2N(CH 3)3][Ti2(OMe)9] (3). A face-shared bioctahedral solid state structure for anion Ti2(OMe) 9- is proposed based on its NMR spectroscopic properties.","Made available in DSpace on 2011-05-07T12:17:27Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9503209.pdf: 2964140 bytes, checksum: 14cc5ec3fbe88c13c767ad06303eda51 (MD5) Previous issue date: 1994","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:39:12Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:16:27-05:00 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":["Low-nuclearity titanium alkoxides and their rhodium derivatives"]}]}],"canonical_facts":{"dc:contributor":["Klemperer, Walter G."],"dc:creator":["Hao, Jinling"],"dc:date":["2011-05-07T12:17:27Z","10000-01-01","1994"],"dc:description":["The reaction of Ti(OPri)4 with 0.078 equiv. of 10 atom% 17O enriched water and 0.6 equiv. of MeOH in i-PrOH solution gave [Ti3O](OPr i)9(OMe) (1). A single crystal X-ray diffraction study of this material indicated that 1 contains two crystallographically-independent Ti3(mu3-O)(mu3-OMe)(mu2-OPr i)3(OPri)6 molecules. The analogous molecule [Ti3O[(OPri)10 (1a) was generated in solution by hydrolysis of Ti(OPri)4 with 0.02 equiv. of water in i-PrOH, and identified using 17O, 13C{1H}, and 1H NMR techniques. Variable temperature NMR spectroscopic studies show that 1 retains its solid state structure at low temperature. It decomposes quickly at room temperature, however, to form Ti(OMe)x(OPr i)4-x, and other polyoxotitanates. 1 has the lowest stability toward parent alcohol and inert hydrocarbon solvents among all known titanium polyoxoalkoxides.","The reaction of [Rh(COD)(OH)]2 with 3 equiv. of Ti(OPr n)4 affords [Rh(COD)]2Ti(OPrn) 6 (2). An X-ray diffraction study indicates that 2 adopts a butterfly structure with two Rh(COD) acting as wings. In solution, 2 exists in equilibrium with [Rh(COD)(OPrn)] 2 (2a), and Ti(OPrn)4. 2a can also be prepared from the reaction of [Rh(COD)(OH)]2 with one equiv. of Ti(OPrn)4.","The reaction of Ti(OMe)4 with 0.63 equiv. of [C6H 5CH2N(CH3)3]OCH3 in toluene/methanol gave analytically-pure [C6H5CH2N(CH 3)3][Ti2(OMe)9] (3). A face-shared bioctahedral solid state structure for anion Ti2(OMe) 9- is proposed based on its NMR spectroscopic properties.","Made available in DSpace on 2011-05-07T12:17:27Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9503209.pdf: 2964140 bytes, checksum: 14cc5ec3fbe88c13c767ad06303eda51 (MD5) Previous issue date: 1994","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:39:12Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:16:27-05:00 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":["AAI9503209","(UMI)AAI9503209","http://hdl.handle.net/2142/19753"],"dc:language":["eng"],"dc:rights":["Copyright 1994 Hao, Jinling"],"dc:subject":["Chemistry, Inorganic","Chemistry, Physical"],"dc:title":["Low-nuclearity titanium alkoxides and their rhodium derivatives"],"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":"2026-07-22T22:25:14Z"}