Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance upgrade on Thursday 4th of May 2017 from 8.00am to 9.00am (BST).

During this time our websites will be offline temporarily. If you have any questions please use the feedback button on this page. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 38, 2009
Previous Article Next Article

Bimetallic complexes based on carboxylate and xanthate ligands: Synthesis and electrochemical investigations

Author affiliations

Abstract

The homobimetallic ruthenium(II) and osmium(II) complexes [{RuR(CO)(PPh3)2}2(S2COCH2C6H4CH2OCS2)] (R = CH[double bond, length as m-dash]CHBut, CH[double bond, length as m-dash]CHC6H4Me-4, C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh, CH[double bond, length as m-dash]CHCPh2OH) and [{Os(CH[double bond, length as m-dash]CHC6H4Me-4)(CO)(PPh3)2}2(S2COCH2C6H4CH2OCS2)] form readily from the reactions of [MRCl(CO)(BTD)(PPh3)2] (M = Ru or Os; BTD = 2,1,3-benzothiadiazole) with the dixanthate KS2COCH2C6H4CH2OCS2K. Addition of KS2COCH2C6H4CH2OCS2K to two equivalents of cis-[RuCl2(dppm)2] leads to the formation of [{(dppm)2Ru}2(S2COCH2C6H4CH2OCS2)]2+. The benzoate complexes [RuR{O2CC6H4(CH2OH)-4}(CO)(PPh3)2] (R = CH[double bond, length as m-dash]CHBut, CH[double bond, length as m-dash]CHC6H4Me-4, C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh) are obtained by treatment of [RuRCl(CO)(BTD)(PPh3)2] with 4-(hydroxymethyl)benzoic acid in the presence of base. Reaction of [RuHCl(CO)(PPh3)3] or [RuRCl(CO)(BTD)(PPh3)2] with 4-(hydroxymethyl)benzoic acid in the absence of base leads to formation of the chloride analogue [RuCl{O2CC6H4(CH2OH)-4}(CO)(PPh3)2]. The unsymmetrical complex [{Ru(CH[double bond, length as m-dash]CHC6H4Me-4)(CO)(PPh3)2}2(O2CC6H4CH2OCS2)] forms from the sequential treatment of [Ru(CH[double bond, length as m-dash]CHC6H4Me-4){O2CC6H4(CH2OH)-4}(CO)(PPh3)2] with base, CS2 and [Ru(CH[double bond, length as m-dash]CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2]. The new mixed-donor xanthate-carboxylate ligand, KO2CC6H4CH2OCS2K is formed by treatment of 4-(hydroxymethyl)benzoic acid with excess KOH and two equivalents of carbon disulfide. This ligand reacts with two equivalents of [Ru(CH[double bond, length as m-dash]CHC6H4Me-4)Cl(BTD)(CO)(PPh3)2] or cis-[RuCl2(dppm)2] to yield [{(dppm)2Ru}2(O2CC6H4CH2OCS2)]2+ or [{Ru(CH[double bond, length as m-dash]CHC6H4Me-4)(CO)(PPh3)2}2(O2CC6H4CH2OCS2)], respectively. Electrochemical experiments are also reported in which communication between the metal centres is investigated.

Graphical abstract: Bimetallic complexes based on carboxylate and xanthate ligands: Synthesis and electrochemical investigations

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 28 Jan 2009, accepted on 03 Apr 2009 and first published on 15 May 2009


Article type: Paper
DOI: 10.1039/B901822K
Citation: Dalton Trans., 2009, 7891-7901
  •   Request permissions

    Bimetallic complexes based on carboxylate and xanthate ligands: Synthesis and electrochemical investigations

    Y. H. Lin, N. H. Leung, K. B. Holt, A. L. Thompson and J. D. E. T. Wilton-Ely, Dalton Trans., 2009, 7891
    DOI: 10.1039/B901822K

Search articles by author