{"id":{"repo_id":"nus","oai_identifier":"oai:scholarbank.nus.edu.sg:10635/27679"},"canonical_url":"https://search.dev.ndltd.org/etd/nus/oai:scholarbank.nus.edu.sg:10635/27679","repository":{"repo_id":"nus","name":"National University of Singapore","base_url":"https://scholarbank.nus.edu.sg/oai/request"},"display":{"title":"Eta5-pentamethylcyclopentadienyl ruthenium complexes containing sulfur ligands","abstract":"The ambient temperature reactions of [Cp*RuCl2]2 towards organic substrates, (i) [Me2NC(S)S]2 and (ii) [Et2NC(S)S]2, isopropylxanthic disulfide (iii) [iPrOC(S)S]2 and bis(thiophosphoryl)disulfide (iv) [(iPrO)2P(S)S]2 produced air-stable Cp*Ru(S2CNR2)Cl2 (R = Me, 2.1; R = Et, 2.2), Cp*Ru(S2COiPr)Cl2 (2.3) and air-sensitive Cp*Ru(S2P(OiPr)2)Cl2 (2.4), respectively. The reactions of 2.1, 2.2 and 2.3 with Na(S)SCNEt2 gave Cp*Ru(S2CNMe2)(S2CNEt2)]Cl (2.5), [Cp*Ru(S2CNEt2)2]Cl (2.6), Cp*Ru(S2CNEt2)(S2CO) (2.8), respectively, and with K(S)SCOiPr gave Cp*Ru(S2CNMe2)(S2CO) (2.7), Cp*Ru(S2CNEt2)(S2CO) (2.8) and Cp*Ru(S2COiPr)(S2CO) (2.9), respectively. The reactivity of 2.1 towards phosphines (PPh3, PPhMe2 and PMe3) gave [Cp*Ru(S2CNMe2)(PPh3)Cl]Cl (2.10), Cp*Ru(S2CNMe2)(PPhMe2)Cl][PF6] (2.11) and [Cp*Ru(S2CNMe2)(PMe3)Cl][BPh4] (2.12). However, 2.3 reacted with PPh3 to give a different product Cp*Ru(S2COiPr)(PPh3) (2.13). Complex 2.1 underwent ligand exchange with the CpCr(CO)3. radical to yield Cp*Ru(S2CNMe2)(CO) (2.14) and CpCrCl2(CH3CN) and it formed [Cp*Ru(S2CNMe2)(SCH2CH2S)] (2.15) with the sodium salt of ethane-1,2-dithiolate. Complex 2.15 was reacted with groups 10 and 11 metal fragments Ni(PPh3)2Cl2, Pt(PPh3)2Cl2 and Au(PPh3)Cl to yield {Cp*Ru(S2CNMe2)(SCH2CH2S)]2Ni}(PF6)2 (2.16), [Cp*Ru(S2CNMe2)(S(CH2)2S) Pt(PPh3)2](PF6)2 (2.17) and [Cp*Ru(S2CNMe2)(SCH2CH2S)Au(PPh3)Cl] (2.18), respectively. The formal oxidation state of ruthenium in all of the products was IV except for 2.13 and 2.14.","abstract_html":"The ambient temperature reactions of [Cp*RuCl2]2 towards organic substrates, (i) [Me2NC(S)S]2 and (ii) [Et2NC(S)S]2, isopropylxanthic disulfide (iii) [iPrOC(S)S]2 and bis(thiophosphoryl)disulfide (iv) [(iPrO)2P(S)S]2 produced air-stable Cp*Ru(S2CNR2)Cl2 (R = Me, 2.1; R = Et, 2.2), Cp*Ru(S2COiPr)Cl2 (2.3) and air-sensitive Cp*Ru(S2P(OiPr)2)Cl2 (2.4), respectively. The reactions of 2.1, 2.2 and 2.3 with Na(S)SCNEt2 gave Cp*Ru(S2CNMe2)(S2CNEt2)]Cl (2.5), [Cp*Ru(S2CNEt2)2]Cl (2.6), Cp*Ru(S2CNEt2)(S2CO) (2.8), respectively, and with K(S)SCOiPr gave Cp*Ru(S2CNMe2)(S2CO) (2.7), Cp*Ru(S2CNEt2)(S2CO) (2.8) and Cp*Ru(S2COiPr)(S2CO) (2.9), respectively. The reactivity of 2.1 towards phosphines (PPh3, PPhMe2 and PMe3) gave [Cp*Ru(S2CNMe2)(PPh3)Cl]Cl (2.10), Cp*Ru(S2CNMe2)(PPhMe2)Cl][PF6] (2.11) and [Cp*Ru(S2CNMe2)(PMe3)Cl][BPh4] (2.12). However, 2.3 reacted with PPh3 to give a different product Cp*Ru(S2COiPr)(PPh3) (2.13). Complex 2.1 underwent ligand exchange with the CpCr(CO)3. radical to yield Cp*Ru(S2CNMe2)(CO) (2.14) and CpCrCl2(CH3CN) and it formed [Cp*Ru(S2CNMe2)(SCH2CH2S)] (2.15) with the sodium salt of ethane-1,2-dithiolate. Complex 2.15 was reacted with groups 10 and 11 metal fragments Ni(PPh3)2Cl2, Pt(PPh3)2Cl2 and Au(PPh3)Cl to yield {Cp*Ru(S2CNMe2)(SCH2CH2S)]2Ni}(PF6)2 (2.16), [Cp*Ru(S2CNMe2)(S(CH2)2S) Pt(PPh3)2](PF6)2 (2.17) and [Cp*Ru(S2CNMe2)(SCH2CH2S)Au(PPh3)Cl] (2.18), respectively. The formal oxidation state of ruthenium in all of the products was IV except for 2.13 and 2.14.","abstract_has_math":false,"creators":["TAY PHUAY LENG, ELAINE"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2004,"date_issued":"2004-10-04","date_published":"2004-10-04","updated_at":"2026-07-24T03:31:38Z","subjects":["pentamethylcyclopentadienyl, ruthenium, dithiocarbamate, xanthate"],"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":["TAY PHUAY LENG, ELAINE"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["2004-10-04"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://scholarbank.nus.edu.sg/handle/10635/27679"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["pentamethylcyclopentadienyl, ruthenium, dithiocarbamate, xanthate"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://scholarbank.nus.edu.sg/bitstreams/f66396d9-e83e-418a-a577-6cf6ec4caf58/download","https://scholarbank.nus.edu.sg/bitstreams/c43993d7-d0fe-4bc2-a76e-e61e7cb9ec39/download"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The ambient temperature reactions of [Cp*RuCl2]2 towards organic substrates, (i) [Me2NC(S)S]2 and (ii) [Et2NC(S)S]2, isopropylxanthic disulfide (iii) [iPrOC(S)S]2 and bis(thiophosphoryl)disulfide (iv) [(iPrO)2P(S)S]2 produced air-stable Cp*Ru(S2CNR2)Cl2 (R = Me, 2.1; R = Et, 2.2), Cp*Ru(S2COiPr)Cl2 (2.3) and air-sensitive Cp*Ru(S2P(OiPr)2)Cl2 (2.4), respectively. The reactions of 2.1, 2.2 and 2.3 with Na(S)SCNEt2 gave Cp*Ru(S2CNMe2)(S2CNEt2)]Cl (2.5), [Cp*Ru(S2CNEt2)2]Cl (2.6), Cp*Ru(S2CNEt2)(S2CO) (2.8), respectively, and with K(S)SCOiPr gave Cp*Ru(S2CNMe2)(S2CO) (2.7), Cp*Ru(S2CNEt2)(S2CO) (2.8) and Cp*Ru(S2COiPr)(S2CO) (2.9), respectively. The reactivity of 2.1 towards phosphines (PPh3, PPhMe2 and PMe3) gave [Cp*Ru(S2CNMe2)(PPh3)Cl]Cl (2.10), Cp*Ru(S2CNMe2)(PPhMe2)Cl][PF6] (2.11) and [Cp*Ru(S2CNMe2)(PMe3)Cl][BPh4] (2.12). However, 2.3 reacted with PPh3 to give a different product Cp*Ru(S2COiPr)(PPh3) (2.13). Complex 2.1 underwent ligand exchange with the CpCr(CO)3. radical to yield Cp*Ru(S2CNMe2)(CO) (2.14) and CpCrCl2(CH3CN) and it formed [Cp*Ru(S2CNMe2)(SCH2CH2S)] (2.15) with the sodium salt of ethane-1,2-dithiolate. Complex 2.15 was reacted with groups 10 and 11 metal fragments Ni(PPh3)2Cl2, Pt(PPh3)2Cl2 and Au(PPh3)Cl to yield {Cp*Ru(S2CNMe2)(SCH2CH2S)]2Ni}(PF6)2 (2.16), [Cp*Ru(S2CNMe2)(S(CH2)2S) Pt(PPh3)2](PF6)2 (2.17) and [Cp*Ru(S2CNMe2)(SCH2CH2S)Au(PPh3)Cl] (2.18), respectively. The formal oxidation state of ruthenium in all of the products was IV except for 2.13 and 2.14."]},{"key":"dc:format.checksum.md5","label":"Dc Format Checksum Md5","values":["680962aaaf98af5aca6d5ca6f54a1110","c88364b71bee3fc96f4511c0f2c8b86e","721f9aee2da84a26da2f7d858618a1e0","8cd4312b89b56e276ba1dad905838f7d"]},{"key":"dc:title","label":"Title","values":["Eta5-pentamethylcyclopentadienyl ruthenium complexes containing sulfur ligands"]}]}],"canonical_facts":{"dc:creator":["TAY PHUAY LENG, ELAINE"],"dc:date.issued":["2004-10-04"],"dc:description.abstract":["The ambient temperature reactions of [Cp*RuCl2]2 towards organic substrates, (i) [Me2NC(S)S]2 and (ii) [Et2NC(S)S]2, isopropylxanthic disulfide (iii) [iPrOC(S)S]2 and bis(thiophosphoryl)disulfide (iv) [(iPrO)2P(S)S]2 produced air-stable Cp*Ru(S2CNR2)Cl2 (R = Me, 2.1; R = Et, 2.2), Cp*Ru(S2COiPr)Cl2 (2.3) and air-sensitive Cp*Ru(S2P(OiPr)2)Cl2 (2.4), respectively. The reactions of 2.1, 2.2 and 2.3 with Na(S)SCNEt2 gave Cp*Ru(S2CNMe2)(S2CNEt2)]Cl (2.5), [Cp*Ru(S2CNEt2)2]Cl (2.6), Cp*Ru(S2CNEt2)(S2CO) (2.8), respectively, and with K(S)SCOiPr gave Cp*Ru(S2CNMe2)(S2CO) (2.7), Cp*Ru(S2CNEt2)(S2CO) (2.8) and Cp*Ru(S2COiPr)(S2CO) (2.9), respectively. The reactivity of 2.1 towards phosphines (PPh3, PPhMe2 and PMe3) gave [Cp*Ru(S2CNMe2)(PPh3)Cl]Cl (2.10), Cp*Ru(S2CNMe2)(PPhMe2)Cl][PF6] (2.11) and [Cp*Ru(S2CNMe2)(PMe3)Cl][BPh4] (2.12). However, 2.3 reacted with PPh3 to give a different product Cp*Ru(S2COiPr)(PPh3) (2.13). Complex 2.1 underwent ligand exchange with the CpCr(CO)3. radical to yield Cp*Ru(S2CNMe2)(CO) (2.14) and CpCrCl2(CH3CN) and it formed [Cp*Ru(S2CNMe2)(SCH2CH2S)] (2.15) with the sodium salt of ethane-1,2-dithiolate. Complex 2.15 was reacted with groups 10 and 11 metal fragments Ni(PPh3)2Cl2, Pt(PPh3)2Cl2 and Au(PPh3)Cl to yield {Cp*Ru(S2CNMe2)(SCH2CH2S)]2Ni}(PF6)2 (2.16), [Cp*Ru(S2CNMe2)(S(CH2)2S) Pt(PPh3)2](PF6)2 (2.17) and [Cp*Ru(S2CNMe2)(SCH2CH2S)Au(PPh3)Cl] (2.18), respectively. The formal oxidation state of ruthenium in all of the products was IV except for 2.13 and 2.14."],"dc:format.checksum.md5":["680962aaaf98af5aca6d5ca6f54a1110","c88364b71bee3fc96f4511c0f2c8b86e","721f9aee2da84a26da2f7d858618a1e0","8cd4312b89b56e276ba1dad905838f7d"],"dc:identifier.uri":["https://scholarbank.nus.edu.sg/bitstreams/f66396d9-e83e-418a-a577-6cf6ec4caf58/download","https://scholarbank.nus.edu.sg/bitstreams/c43993d7-d0fe-4bc2-a76e-e61e7cb9ec39/download"],"dc:relation.isreferencedby":["https://scholarbank.nus.edu.sg/handle/10635/27679"],"dc:subject":["pentamethylcyclopentadienyl, ruthenium, dithiocarbamate, xanthate"],"dc:title":["Eta5-pentamethylcyclopentadienyl ruthenium complexes containing sulfur ligands"],"dc:type":["Thesis"]},"updated_at":"2026-07-24T03:31:38Z"}