Eta5-pentamethylcyclopentadienyl ruthenium complexes containing sulfur ligands
type: CreativeWork
description: 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: 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.
author: TAY PHUAY LENG, ELAINE
keywords: pentamethylcyclopentadienyl, ruthenium, dithiocarbamate, xanthate
date published: 2004-10-04
date modified: 2026-07-24T03:31:38Z
provider: National University of Singapore
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: National University of Singapore