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

Lin, YH; Leung, NH; Holt, KB; Thompson, AL; Wilton-Ely, JDET; (2009) Bimetallic complexes based on carboxylate and xanthate ligands: Synthesis and electrochemical investigations. DALTON T (38) 7891 - 7901. 10.1039/b901822k.

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Abstract

The homobimetallic ruthenium(II) and osmium(II) complexes [{RuR(CO)(PPh3)(2)}(2)-(S2COCH2C6H4CH2OCS2)] (R = CH= CHBut, CH=CHC6H4Me-4, C(C CPh)=CHPh, CH=CHCPh2OH) and [{Os(CH=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)(2)Ru}(2-)( S2COCH2C6H4CH2OCS2)](2+). The benzoate complexes [RuR{O2CC6H4(CH2OH)-4}(CO)(PPh3)(2)] (R = CH=CHBut, CH= CHC6H4Me-4, C(C CPh)=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= CHC6H4Me-4)(CO)(PPh3)(2)} (2)(O2CC6H4CH2OCS2)] forms from the sequential treatment of [Ru(CH= CHC6H4Me-4){O2CC6H4(CH2OH)-4}(CO)(PPh3)(2)] with base, CS2 and [Ru(CH=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 disul. de. This ligand reacts with two equivalents of [Ru(CH= CHC6H4Me-4) Cl(BTD)(CO)(PPh3)(2)] or cis-[RuCl2(dppm)(2)] to yield [{(dppm)(2)Ru}(2)-(O2CC6H4CH2OCS2)](2+) or [{Ru(CH=CHC6H4Me-4)(CO)(PPh3)(2)}(2)(O2CC6H4CH2OCS2)], respectively. Electrochemical experiments are also reported in which communication between the metal centres is investigated.

Type:Article
Title:Bimetallic complexes based on carboxylate and xanthate ligands: Synthesis and electrochemical investigations
DOI:10.1039/b901822k
Keywords:MIXED-DONOR LIGANDS, CARBENE RUTHENIUM(II) COMPLEXES, DIYNE COORDINATION CHEMISTRY, SIGMA-ORGANYL COMPLEXES, RAY CRYSTAL-STRUCTURE, 2 ALKENYL FRAGMENTS, INSERTION REACTIONS, OSMIUM COMPLEXES, ALLENYLIDENE LIGAND, DIHYDROGEN COMPLEX
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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