{"id":{"repo_id":"ubc","oai_identifier":"oai:circle.library.ubc.ca:2429/2203"},"canonical_url":"https://search.dev.ndltd.org/etd/ubc/oai:circle.library.ubc.ca:2429/2203","repository":{"repo_id":"ubc","name":"University of British Columbia","base_url":"http://circle.library.ubc.ca/oai/request"},"display":{"title":"Heterocumulene insertions with group 6 Diaryl Nitrosyl complexes","abstract":"Treatment of the 16-electron complexes Cp*M(NO)(aryl)2 (Cp* = i5-05Me5; M =Mo, W; aryl = phenyl, o-tolyl, p-tolyl) with the heterocumulenes carbon dioxide, p-tolylisocyanate, and carbon disulfide leads to the i2-carboxylate-, i2-amide-, and i2-thiocarboxylate-containing complexes, respectively, in 10-50% yields. Treatment with a fourth member of the heterocumulene class, diphenylketene, does not result in an isolable inserted complex, although spectroscopic data suggest that insertion has taken place. Cp*M(NO)(aryl)2 complexes thus insert one heterocumulene molecule into a metal-aryl bond; the other metal-aryl bond is inert to further insertion. The resulting complexes are thermally stable and air-stable, and can be described as being 18-electron species. Protonolysis of the representative heterocumulene-inserted complex Cp*W(NO){112-N(p-tol)C(0)Ph}Ph releases the functionalized heterocumulene molecule, p-tolylbenzamide.All new complexes have been fully characterized by conventional methods. In addition, Cp*W(NO)(r12-S2CPh)Ph reacts with the Lewis base trimethylphosphine to form Cp*W(NO){112-S2C(PMe3)Ph}Ph which contains a zwitterionic phosphonium-betaine ligand. X-ray crystallographic studies of Cp*W(NO){1.12-82C(PMe3)Ph}Ph and Cp*W(N0)(112-0NPh)(NPh)Ph are reported and discussed.","abstract_html":"Treatment of the 16-electron complexes Cp*M(NO)(aryl)2 (Cp* = i5-05Me5; M =Mo, W; aryl = phenyl, o-tolyl, p-tolyl) with the heterocumulenes carbon dioxide, p-tolylisocyanate, and carbon disulfide leads to the i2-carboxylate-, i2-amide-, and i2-thiocarboxylate-containing complexes, respectively, in 10-50% yields. Treatment with a fourth member of the heterocumulene class, diphenylketene, does not result in an isolable inserted complex, although spectroscopic data suggest that insertion has taken place. Cp*M(NO)(aryl)2 complexes thus insert one heterocumulene molecule into a metal-aryl bond; the other metal-aryl bond is inert to further insertion. The resulting complexes are thermally stable and air-stable, and can be described as being 18-electron species. Protonolysis of the representative heterocumulene-inserted complex Cp*W(NO){112-N(p-tol)C(0)Ph}Ph releases the functionalized heterocumulene molecule, p-tolylbenzamide.All new complexes have been fully characterized by conventional methods. In addition, Cp*W(NO)(r12-S2CPh)Ph reacts with the Lewis base trimethylphosphine to form Cp*W(NO){112-S2C(PMe3)Ph}Ph which contains a zwitterionic phosphonium-betaine ligand. X-ray crystallographic studies of Cp*W(NO){1.12-82C(PMe3)Ph}Ph and Cp*W(N0)(112-0NPh)(NPh)Ph are reported and discussed.","abstract_has_math":false,"creators":["Brouwer, Eric B."],"institution":"University of British Columbia","degree_name":"Master of Science - MSc","degree_level":"master's","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1992,"date_issued":"1992","date_published":"1992","updated_at":"2026-07-24T05:07:35Z","subjects":[],"languages":["eng"],"rights":["For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2429/2203","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Brouwer, Eric B."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["1992"]},{"key":"dc:publisher","label":"Institution","values":["University of British Columbia"]},{"key":"dc:type","label":"Dc Type","values":["Text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["master's"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Science - MSc"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of British Columbia"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2429/2203","http://circle.library.ubc.ca/bitstream/2429/2203/1/ubc_1992_fall_brouwer_eric.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Treatment of the 16-electron complexes Cp*M(NO)(aryl)2 (Cp* = i5-05Me5; M =Mo, W; aryl = phenyl, o-tolyl, p-tolyl) with the heterocumulenes carbon dioxide, p-tolylisocyanate, and carbon disulfide leads to the i2-carboxylate-, i2-amide-, and i2-thiocarboxylate-containing complexes, respectively, in 10-50% yields. Treatment with a fourth member of the heterocumulene class, diphenylketene, does not result in an isolable inserted complex, although spectroscopic data suggest that insertion has taken place. Cp*M(NO)(aryl)2 complexes thus insert one heterocumulene molecule into a metal-aryl bond; the other metal-aryl bond is inert to further insertion. The resulting complexes are thermally stable and air-stable, and can be described as being 18-electron species. Protonolysis of the representative heterocumulene-inserted complex Cp*W(NO){112-N(p-tol)C(0)Ph}Ph releases the functionalized heterocumulene molecule, p-tolylbenzamide.All new complexes have been fully characterized by conventional methods. In addition, Cp*W(NO)(r12-S2CPh)Ph reacts with the Lewis base trimethylphosphine to form Cp*W(NO){112-S2C(PMe3)Ph}Ph which contains a zwitterionic phosphonium-betaine ligand. X-ray crystallographic studies of Cp*W(NO){1.12-82C(PMe3)Ph}Ph and Cp*W(N0)(112-0NPh)(NPh)Ph are reported and discussed."]},{"key":"dc:format","label":"Dc Format","values":["5041389","application/pdf"]},{"key":"dc:title","label":"Title","values":["Heterocumulene insertions with group 6 Diaryl Nitrosyl complexes"]}]}],"canonical_facts":{"dc:creator":["Brouwer, Eric B."],"dc:date":["1992"],"dc:description":["Treatment of the 16-electron complexes Cp*M(NO)(aryl)2 (Cp* = i5-05Me5; M =Mo, W; aryl = phenyl, o-tolyl, p-tolyl) with the heterocumulenes carbon dioxide, p-tolylisocyanate, and carbon disulfide leads to the i2-carboxylate-, i2-amide-, and i2-thiocarboxylate-containing complexes, respectively, in 10-50% yields. Treatment with a fourth member of the heterocumulene class, diphenylketene, does not result in an isolable inserted complex, although spectroscopic data suggest that insertion has taken place. Cp*M(NO)(aryl)2 complexes thus insert one heterocumulene molecule into a metal-aryl bond; the other metal-aryl bond is inert to further insertion. The resulting complexes are thermally stable and air-stable, and can be described as being 18-electron species. Protonolysis of the representative heterocumulene-inserted complex Cp*W(NO){112-N(p-tol)C(0)Ph}Ph releases the functionalized heterocumulene molecule, p-tolylbenzamide.All new complexes have been fully characterized by conventional methods. In addition, Cp*W(NO)(r12-S2CPh)Ph reacts with the Lewis base trimethylphosphine to form Cp*W(NO){112-S2C(PMe3)Ph}Ph which contains a zwitterionic phosphonium-betaine ligand. X-ray crystallographic studies of Cp*W(NO){1.12-82C(PMe3)Ph}Ph and Cp*W(N0)(112-0NPh)(NPh)Ph are reported and discussed."],"dc:format":["5041389","application/pdf"],"dc:identifier":["http://hdl.handle.net/2429/2203","http://circle.library.ubc.ca/bitstream/2429/2203/1/ubc_1992_fall_brouwer_eric.pdf"],"dc:language":["eng"],"dc:publisher":["University of British Columbia"],"dc:rights":["For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use."],"dc:title":["Heterocumulene insertions with group 6 Diaryl Nitrosyl complexes"],"dc:type":["Text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["master's"],"thesis:degree_name":["Master of Science - MSc"],"thesis:institution_name":["University of British Columbia"]},"updated_at":"2026-07-24T05:07:35Z"}