{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/22380"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/22380","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"High oxidation state organometallic and coordination chemistry: The synthesis and reactivity of nitridoosmium(VI) thiolates and alkoxides","abstract":"Transition metal-thioaldehyde complexes were reviewed in Chapter 1. A series of organoosmium(VI) thiolate complexes, (Os(N)$\\rm(CH\\sb2SiMe\\sb3)\\sb2(\\mu$-SR) $\\sb2$ (R = Et, CMe$\\sb3,$ CHMe$\\sb2,$ CH$\\sb2$CHMe$\\sb2,$ CH$\\sb2$Ph), and the tetraalkoxide and tetrathiolate complexes $\\rm\\lbrack PPh\\sb4\\rbrack\\lbrack Os(N)(ECH\\sb2Ph)\\sb4\\rbrack$ (E = O, S) were synthesized and characterized. Thermolysis of the tetrathiolate forms benzyl disulfide while the tetraalkoxide complex produces benzaldehyde and benzyl alcohol in a 1:1 ratio upon heating. This first reported example of $\\beta$-H elimination from an osmium-alkoxide complex is presented in Chapter 2. The reactivity of the cationic, solvate complex $\\rm\\lbrack Os(N)(CH\\sb2SiMe\\sb3)\\sb2(NC\\sb5H\\sb5)\\sb2\\rbrack\\lbrack BF\\sb4\\rbrack$ with a variety of anionic ligands is reported in Chapter 3. Reactions of this solvate complex with monodentate, anionic ligands yield binuclear or trinuclear complexes, whereas reactions with multidentate and facially-coordinant, anionic ligands, such as indenyl and tris(pyrazolyl)borate, yield mononuclear complexes. The synthesis of several nitridoosmium and nitridoruthenium(VI)-dithiolene complexes is reported in Chapter 4. Included among these are the first organometallic dithiolene complexes possessing multiply-bonded ligands.","abstract_html":"Transition metal-thioaldehyde complexes were reviewed in Chapter 1. A series of organoosmium(VI) thiolate complexes, (Os(N)<span class=\"etd-inline-math\">\\rm(CH\\sb2SiMe\\sb3)\\sb2(&mu;</span>-SR) $\\sb2$ (R = Et, CMe$\\sb3,$ CHMe$\\sb2,$ CH$\\sb2$CHMe$\\sb2,$ CH$\\sb2$Ph), and the tetraalkoxide and tetrathiolate complexes $\\rm\\lbrack PPh\\sb4\\rbrack\\lbrack Os(N)(ECH\\sb2Ph)\\sb4\\rbrack$ (E = O, S) were synthesized and characterized. Thermolysis of the tetrathiolate forms benzyl disulfide while the tetraalkoxide complex produces benzaldehyde and benzyl alcohol in a 1:1 ratio upon heating. This first reported example of <span class=\"etd-inline-math\">&beta;</span>-H elimination from an osmium-alkoxide complex is presented in Chapter 2. The reactivity of the cationic, solvate complex $\\rm\\lbrack Os(N)(CH\\sb2SiMe\\sb3)\\sb2(NC\\sb5H\\sb5)\\sb2\\rbrack\\lbrack BF\\sb4\\rbrack$ with a variety of anionic ligands is reported in Chapter 3. Reactions of this solvate complex with monodentate, anionic ligands yield binuclear or trinuclear complexes, whereas reactions with multidentate and facially-coordinant, anionic ligands, such as indenyl and tris(pyrazolyl)borate, yield mononuclear complexes. The synthesis of several nitridoosmium and nitridoruthenium(VI)-dithiolene complexes is reported in Chapter 4. Included among these are the first organometallic dithiolene complexes possessing multiply-bonded ligands.","abstract_has_math":true,"creators":["Reinerth, William Alan"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Shapley, Patricia A."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:38:01Z","date_published":"2011-05-07T13:38:01Z","updated_at":"2026-07-22T22:25:19Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1996 Reinerth, William Alan"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591088366","AAI9702651","(UMI)AAI9702651"],"render_values":[{"text":"9780591088366","href":null,"code":true},{"text":"AAI9702651","href":null,"code":true},{"text":"(UMI)AAI9702651","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/22380","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Shapley, Patricia A."]},{"key":"dc:creator","label":"Author","values":["Reinerth, William Alan"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:38:01Z","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"]}]},{"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 Reinerth, William Alan"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591088366","AAI9702651","(UMI)AAI9702651","http://hdl.handle.net/2142/22380"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Transition metal-thioaldehyde complexes were reviewed in Chapter 1. A series of organoosmium(VI) thiolate complexes, (Os(N)$\\rm(CH\\sb2SiMe\\sb3)\\sb2(\\mu$-SR) $\\sb2$ (R = Et, CMe$\\sb3,$ CHMe$\\sb2,$ CH$\\sb2$CHMe$\\sb2,$ CH$\\sb2$Ph), and the tetraalkoxide and tetrathiolate complexes $\\rm\\lbrack PPh\\sb4\\rbrack\\lbrack Os(N)(ECH\\sb2Ph)\\sb4\\rbrack$ (E = O, S) were synthesized and characterized. Thermolysis of the tetrathiolate forms benzyl disulfide while the tetraalkoxide complex produces benzaldehyde and benzyl alcohol in a 1:1 ratio upon heating. This first reported example of $\\beta$-H elimination from an osmium-alkoxide complex is presented in Chapter 2. The reactivity of the cationic, solvate complex $\\rm\\lbrack Os(N)(CH\\sb2SiMe\\sb3)\\sb2(NC\\sb5H\\sb5)\\sb2\\rbrack\\lbrack BF\\sb4\\rbrack$ with a variety of anionic ligands is reported in Chapter 3. Reactions of this solvate complex with monodentate, anionic ligands yield binuclear or trinuclear complexes, whereas reactions with multidentate and facially-coordinant, anionic ligands, such as indenyl and tris(pyrazolyl)borate, yield mononuclear complexes. The synthesis of several nitridoosmium and nitridoruthenium(VI)-dithiolene complexes is reported in Chapter 4. Included among these are the first organometallic dithiolene complexes possessing multiply-bonded ligands.","Made available in DSpace on 2011-05-07T13:38:01Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702651.pdf: 3705682 bytes, checksum: 6664471bf1ff8a270158e2c9515d6e31 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:57:14Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:26:49-05:00 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":["High oxidation state organometallic and coordination chemistry: The synthesis and reactivity of nitridoosmium(VI) thiolates and alkoxides"]}]}],"canonical_facts":{"dc:contributor":["Shapley, Patricia A."],"dc:creator":["Reinerth, William Alan"],"dc:date":["2011-05-07T13:38:01Z","10000-01-01","1996"],"dc:description":["Transition metal-thioaldehyde complexes were reviewed in Chapter 1. A series of organoosmium(VI) thiolate complexes, (Os(N)$\\rm(CH\\sb2SiMe\\sb3)\\sb2(\\mu$-SR) $\\sb2$ (R = Et, CMe$\\sb3,$ CHMe$\\sb2,$ CH$\\sb2$CHMe$\\sb2,$ CH$\\sb2$Ph), and the tetraalkoxide and tetrathiolate complexes $\\rm\\lbrack PPh\\sb4\\rbrack\\lbrack Os(N)(ECH\\sb2Ph)\\sb4\\rbrack$ (E = O, S) were synthesized and characterized. Thermolysis of the tetrathiolate forms benzyl disulfide while the tetraalkoxide complex produces benzaldehyde and benzyl alcohol in a 1:1 ratio upon heating. This first reported example of $\\beta$-H elimination from an osmium-alkoxide complex is presented in Chapter 2. The reactivity of the cationic, solvate complex $\\rm\\lbrack Os(N)(CH\\sb2SiMe\\sb3)\\sb2(NC\\sb5H\\sb5)\\sb2\\rbrack\\lbrack BF\\sb4\\rbrack$ with a variety of anionic ligands is reported in Chapter 3. Reactions of this solvate complex with monodentate, anionic ligands yield binuclear or trinuclear complexes, whereas reactions with multidentate and facially-coordinant, anionic ligands, such as indenyl and tris(pyrazolyl)borate, yield mononuclear complexes. The synthesis of several nitridoosmium and nitridoruthenium(VI)-dithiolene complexes is reported in Chapter 4. Included among these are the first organometallic dithiolene complexes possessing multiply-bonded ligands.","Made available in DSpace on 2011-05-07T13:38:01Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702651.pdf: 3705682 bytes, checksum: 6664471bf1ff8a270158e2c9515d6e31 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:57:14Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:26:49-05:00 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":["9780591088366","AAI9702651","(UMI)AAI9702651","http://hdl.handle.net/2142/22380"],"dc:language":["eng"],"dc:rights":["Copyright 1996 Reinerth, William Alan"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["High oxidation state organometallic and coordination chemistry: The synthesis and reactivity of nitridoosmium(VI) thiolates and alkoxides"],"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":"2026-07-22T22:25:19Z"}