{"id":{"repo_id":"uwo","oai_identifier":"oai:uwo.scholaris.ca:20.500.14721/29514"},"canonical_url":"https://search.dev.ndltd.org/etd/uwo/oai:uwo.scholaris.ca:20.500.14721/29514","repository":{"repo_id":"uwo","name":"Western University","base_url":"https://uwo.scholaris.ca/server/oai/request"},"display":{"title":"The Reactivity of Ditetrelenes Towards Organophosphorus Oxides","abstract":"The reactivity of tetramesityldisilene 4 and tetramesityldigermene 5 towards organophosphorus oxides was explored in this thesis. The reaction of dialkyl and diarylphosphine oxides and phosphites with ditetrelenes 4 and 5 resulted in a 1,3-addition to form diorganodisilyl and digermyl phosphinites 27, 28, 31, 32 and disilyl phosphites 35 and 36. The 1,3-addition resulted in a mild two electron reduction of the P(V) centre of the phosphine oxide and phosphite to a P(III) centre in the products, without the use of heat or a catalyst. The reaction of organophosphorus oxides provides another example of a main group oxide that can be activated by ditetrelenes 4 and 5 in addition to nitro and sulfonyl containing compounds, CO and CO2. The mechanism for the reaction of diorganophosphorus oxides and phosphites with ditetrelenes 4 and 5 was investigated through deuterium labelling studies and KIE experiments. The mechanism for the formation of disilyl and digermyl phosphinites and phosphites was determined to proceed through a nucleophilic addition. An exchange phenomenon between the OP(pentyl)2 moiety of 32 and an OPPh2 group from diphenylphosphine oxide was discovered and insights into the mechanism of this exchange were obtained.","abstract_html":"The reactivity of tetramesityldisilene 4 and tetramesityldigermene 5 towards organophosphorus oxides was explored in this thesis. The reaction of dialkyl and diarylphosphine oxides and phosphites with ditetrelenes 4 and 5 resulted in a 1,3-addition to form diorganodisilyl and digermyl phosphinites 27, 28, 31, 32 and disilyl phosphites 35 and 36. The 1,3-addition resulted in a mild two electron reduction of the P(V) centre of the phosphine oxide and phosphite to a P(III) centre in the products, without the use of heat or a catalyst. The reaction of organophosphorus oxides provides another example of a main group oxide that can be activated by ditetrelenes 4 and 5 in addition to nitro and sulfonyl containing compounds, CO and CO2. The mechanism for the reaction of diorganophosphorus oxides and phosphites with ditetrelenes 4 and 5 was investigated through deuterium labelling studies and KIE experiments. The mechanism for the formation of disilyl and digermyl phosphinites and phosphites was determined to proceed through a nucleophilic addition. An exchange phenomenon between the OP(pentyl)2 moiety of 32 and an OPPh2 group from diphenylphosphine oxide was discovered and insights into the mechanism of this exchange were obtained.","abstract_has_math":false,"creators":["Belcina, Maissa"],"institution":"The University of Western Ontario","degree_name":"M Sc","degree_level":null,"degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":["Baines, Kim M."],"committee_chairs":[],"committee_members":[],"year":2019,"date_issued":"2019-08-09","date_published":"2019-08-09","updated_at":"2026-07-27T21:55:54Z","subjects":["Group 14","silicon","germanium","disilene","digermene","organophosphorus oxides"],"languages":["en_ca"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/20.500.14721/29514","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Baines, Kim M."]},{"key":"dc:creator","label":"Author","values":["Belcina, Maissa"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2025-07-10T18:32:13Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2025-07-10T18:32:13Z"]},{"key":"dc:date.issued","label":"Date","values":["2019-08-09"]},{"key":"dc:publisher","label":"Institution","values":["The University of Western Ontario"]},{"key":"dc:type","label":"Dc Type","values":["thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_name","label":"Degree Name","values":["M Sc"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Group 14","silicon","germanium","disilene","digermene","organophosphorus oxides"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en_ca"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/20.500.14721/29514"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The thesis cover page in the PDF document includes references to Western University’s previous institutional repository platform, known as Scholarship@Western, and links to that platform (beginning with ir.lib.uwo.ca). In citing or referring to this thesis, use the DOI or handle from this page instead. Sample citation: Author name, \"Thesis title.\" (Year). Western University Open Repository. https://doi.org/10.71858/123456."]},{"key":"dc:description.abstract","label":"Abstract","values":["The reactivity of tetramesityldisilene 4 and tetramesityldigermene 5 towards organophosphorus oxides was explored in this thesis. The reaction of dialkyl and diarylphosphine oxides and phosphites with ditetrelenes 4 and 5 resulted in a 1,3-addition to form diorganodisilyl and digermyl phosphinites 27, 28, 31, 32 and disilyl phosphites 35 and 36. The 1,3-addition resulted in a mild two electron reduction of the P(V) centre of the phosphine oxide and phosphite to a P(III) centre in the products, without the use of heat or a catalyst. The reaction of organophosphorus oxides provides another example of a main group oxide that can be activated by ditetrelenes 4 and 5 in addition to nitro and sulfonyl containing compounds, CO and CO2. The mechanism for the reaction of diorganophosphorus oxides and phosphites with ditetrelenes 4 and 5 was investigated through deuterium labelling studies and KIE experiments. The mechanism for the formation of disilyl and digermyl phosphinites and phosphites was determined to proceed through a nucleophilic addition. An exchange phenomenon between the OP(pentyl)2 moiety of 32 and an OPPh2 group from diphenylphosphine oxide was discovered and insights into the mechanism of this exchange were obtained."]},{"key":"dc:title","label":"Title","values":["The Reactivity of Ditetrelenes Towards Organophosphorus Oxides"]}]}],"canonical_facts":{"dc:contributor.advisor":["Baines, Kim M."],"dc:creator":["Belcina, Maissa"],"dc:date.accessioned":["2025-07-10T18:32:13Z"],"dc:date.available":["2025-07-10T18:32:13Z"],"dc:date.issued":["2019-08-09"],"dc:description":["The thesis cover page in the PDF document includes references to Western University’s previous institutional repository platform, known as Scholarship@Western, and links to that platform (beginning with ir.lib.uwo.ca). In citing or referring to this thesis, use the DOI or handle from this page instead. Sample citation: Author name, \"Thesis title.\" (Year). Western University Open Repository. https://doi.org/10.71858/123456."],"dc:description.abstract":["The reactivity of tetramesityldisilene 4 and tetramesityldigermene 5 towards organophosphorus oxides was explored in this thesis. The reaction of dialkyl and diarylphosphine oxides and phosphites with ditetrelenes 4 and 5 resulted in a 1,3-addition to form diorganodisilyl and digermyl phosphinites 27, 28, 31, 32 and disilyl phosphites 35 and 36. The 1,3-addition resulted in a mild two electron reduction of the P(V) centre of the phosphine oxide and phosphite to a P(III) centre in the products, without the use of heat or a catalyst. The reaction of organophosphorus oxides provides another example of a main group oxide that can be activated by ditetrelenes 4 and 5 in addition to nitro and sulfonyl containing compounds, CO and CO2. The mechanism for the reaction of diorganophosphorus oxides and phosphites with ditetrelenes 4 and 5 was investigated through deuterium labelling studies and KIE experiments. The mechanism for the formation of disilyl and digermyl phosphinites and phosphites was determined to proceed through a nucleophilic addition. An exchange phenomenon between the OP(pentyl)2 moiety of 32 and an OPPh2 group from diphenylphosphine oxide was discovered and insights into the mechanism of this exchange were obtained."],"dc:identifier.uri":["https://hdl.handle.net/20.500.14721/29514"],"dc:language.iso":["en_ca"],"dc:publisher":["The University of Western Ontario"],"dc:subject":["Group 14","silicon","germanium","disilene","digermene","organophosphorus oxides"],"dc:title":["The Reactivity of Ditetrelenes Towards Organophosphorus Oxides"],"dc:type":["thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_name":["M Sc"]},"updated_at":"2026-07-27T21:55:54Z"}