{"id":{"repo_id":"nus","oai_identifier":"oai:scholarbank.nus.edu.sg:10635/16533"},"canonical_url":"https://search.dev.ndltd.org/etd/nus/oai:scholarbank.nus.edu.sg:10635/16533","repository":{"repo_id":"nus","name":"National University of Singapore","base_url":"https://scholarbank.nus.edu.sg/oai/request"},"display":{"title":"Ligand reactivities in platinum and palladium chalcogen complexes","abstract":"In this thesis we shall report on two metalloligands, [Pt2(B5-X)2(dppy)4] and [PtX4(P-P)] (X = S or Se; P-P = 2PPh3 or dppe) and their heterometallic aggregates. The high reactivity of d10 metal-metal bonded complexes towards {PtX4} and {Pt2(B5-S)2} core have been demonstrated through the successful isolation of a number of novel homo- and hetero-polynuclear complexes of [Pt2M2(N<3-S)2(N<-dppy)2(dppy)2(N<-dppm)][PF6]2, [Pd3Pt2(B53-X)2(N<-dppy)4(dppy)4][PF6]3; [PtM2(B53-X)2(P-P)(dppmSe-N:2Se,P4)2][PF6]2 (M= Pd or Pt). The optical limiting properties of the newly synthesized complexes are also reported.An extension of alkylation and oxidation of the {Pt2(B5-S)2} core will also be included. A series of imidazolium and thiazolium ligands have been successfully anchored on the core with further hetero-alkylation using Me2SO4. The dialkylated complexes were mixed with Pd(OAc)2 for Suzuki-Miyaura cross-coupling reactions, giving promising yields. It was also proved that in the presence of lanthanide(III)/scandium(III) salts or strong oxidants, the {Pt2(B5-S)2} core was easily oxidized to [Pt2(B52-S2O2H)(PPh3)4][PF6].","abstract_html":"In this thesis we shall report on two metalloligands, [Pt2(B5-X)2(dppy)4] and [PtX4(P-P)] (X = S or Se; P-P = 2PPh3 or dppe) and their heterometallic aggregates. The high reactivity of d10 metal-metal bonded complexes towards {PtX4} and {Pt2(B5-S)2} core have been demonstrated through the successful isolation of a number of novel homo- and hetero-polynuclear complexes of [Pt2M2(N&lt;3-S)2(N&lt;-dppy)2(dppy)2(N&lt;-dppm)][PF6]2, [Pd3Pt2(B53-X)2(N&lt;-dppy)4(dppy)4][PF6]3; [PtM2(B53-X)2(P-P)(dppmSe-N:2Se,P4)2][PF6]2 (M= Pd or Pt). The optical limiting properties of the newly synthesized complexes are also reported.An extension of alkylation and oxidation of the {Pt2(B5-S)2} core will also be included. A series of imidazolium and thiazolium ligands have been successfully anchored on the core with further hetero-alkylation using Me2SO4. The dialkylated complexes were mixed with Pd(OAc)2 for Suzuki-Miyaura cross-coupling reactions, giving promising yields. It was also proved that in the presence of lanthanide(III)/scandium(III) salts or strong oxidants, the {Pt2(B5-S)2} core was easily oxidized to [Pt2(B52-S2O2H)(PPh3)4][PF6].","abstract_has_math":false,"creators":["LI JINGQIU"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-02-11","date_published":"2009-02-11","updated_at":"2026-07-24T03:33:09Z","subjects":["Platinum, Chalcogen, Ligands"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["LI JINGQIU"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["2009-02-11"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://scholarbank.nus.edu.sg/handle/10635/16533"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Platinum, Chalcogen, Ligands"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://scholarbank.nus.edu.sg/bitstreams/d6996e50-622b-4b8a-b929-5252519e101e/download","https://scholarbank.nus.edu.sg/bitstreams/26b5cdf6-72fa-492d-9f3e-2561ff687a39/download","https://scholarbank.nus.edu.sg/bitstreams/b1d6b8e4-662c-42ea-abfb-0a4ff820a090/download","https://scholarbank.nus.edu.sg/bitstreams/76975128-4c3c-4225-aa79-30c5b9c28a2a/download","https://scholarbank.nus.edu.sg/bitstreams/1c8f3632-a407-458e-a424-5b1eee7bf240/download","https://scholarbank.nus.edu.sg/bitstreams/2d92157e-c8fe-4d79-98aa-f409a16455a8/download","https://scholarbank.nus.edu.sg/bitstreams/abf7d815-568a-4234-b4ae-8c23b80faad7/download","https://scholarbank.nus.edu.sg/bitstreams/8c39c6ee-bf53-4648-90fe-f7e61209a0e1/download","https://scholarbank.nus.edu.sg/bitstreams/6a939057-8897-45f5-b729-a21e2e0f87d0/download","https://scholarbank.nus.edu.sg/bitstreams/c8a48e37-820e-47d7-8d45-8fb57682ea89/download","https://scholarbank.nus.edu.sg/bitstreams/a477b2e2-1dee-4c40-8b5a-39d4b61857b0/download"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["In this thesis we shall report on two metalloligands, [Pt2(B5-X)2(dppy)4] and [PtX4(P-P)] (X = S or Se; P-P = 2PPh3 or dppe) and their heterometallic aggregates. The high reactivity of d10 metal-metal bonded complexes towards {PtX4} and {Pt2(B5-S)2} core have been demonstrated through the successful isolation of a number of novel homo- and hetero-polynuclear complexes of [Pt2M2(N<3-S)2(N<-dppy)2(dppy)2(N<-dppm)][PF6]2, [Pd3Pt2(B53-X)2(N<-dppy)4(dppy)4][PF6]3; [PtM2(B53-X)2(P-P)(dppmSe-N:2Se,P4)2][PF6]2 (M= Pd or Pt). The optical limiting properties of the newly synthesized complexes are also reported.An extension of alkylation and oxidation of the {Pt2(B5-S)2} core will also be included. A series of imidazolium and thiazolium ligands have been successfully anchored on the core with further hetero-alkylation using Me2SO4. The dialkylated complexes were mixed with Pd(OAc)2 for Suzuki-Miyaura cross-coupling reactions, giving promising yields. 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