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Lin YH, Leung NH, Holt KB, Thompson AL, Wilton-Ely JD: Bimetallic complexes based on carboxylate and xanthate ligands: synthesis and electrochemical investigations. Dalton Trans. 2009 Oct 14;(38):7891-901. Epub 2009 May 15.
The homobimetallic ruthenium (II) and osmium (II) complexes [{RuR (CO)(PPh (3))(2)}(2)(S (2) COCH (2) C (6) H (4) CH (2) OCS (2))] (R = CH=CHBu (t), CH=CHC (6) H (4) Me-4, C (C [triple bond] CPh)=CHPh, CH=CHCPh (2) OH) and [{Os (CH=CHC (6) H (4) Me-4)(CO)(PPh (3))(2)}(2)(S (2) COCH (2) C (6) H (4) CH (2) OCS (2)) ] form readily from the reactions of [MRCl (CO)(BTD)(PPh (3))(2)] (M = Ru or Os; BTD = 2,1,3-benzothiadiazole) with the dixanthate KS (2) COCH (2) C (6) H (4) CH (2) OCS (2) K. Addition of KS (2) COCH (2) C (6) H (4) CH (2) OCS (2) K to two equivalents of cis-[RuCl (2)(dppm)(2)] leads to the formation of [{(dppm)(2) Ru}(2)(S (2) COCH (2) C (6) H (4) CH (2) OCS (2))](2+). The benzoate complexes [RuR{O (2) CC (6) H (4)(CH (2) OH)-4}(CO)(PPh (3))(2)] (R = CH=CHBu (t), CH=CHC (6) H (4) Me-4, C (C [triple bond] CPh)=CHPh) are obtained by treatment of [RuRCl (CO)(BTD)(PPh (3))(2)] with 4-(hydroxymethyl) benzoic acid in the presence of base. Reaction of [RuHCl (CO)(PPh (3))(3)] or [RuRCl (CO)(BTD)(PPh (3))(2)] with 4-(hydroxymethyl) benzoic acid in the absence of base leads to formation of the chloride analogue [RuCl{O (2) CC (6) H (4)(CH (2) OH)-4}(CO)(PPh (3))(2)]. The unsymmetrical complex [{Ru (CH=CHC (6) H (4) Me-4)(CO)(PPh (3))(2)}(2)(O (2) CC (6) H (4) CH (2) OCS (2))] forms from the sequential treatment of [Ru (CH=CHC (6) H (4) Me-4){O (2) CC (6) H (4)(CH (2) OH)-4}(CO)(PPh (3))(2)] with base, CS (2) and [Ru (CH=CHC (6) H (4) Me-4) Cl (CO)(BTD)(PPh (3))(2)]. The new mixed-donor xanthate-carboxylate ligand, KO (2) CC (6) H (4) CH (2) OCS (2) K 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=CHC (6) H (4) Me-4) Cl (BTD)(CO)(PPh (3))(2)] or cis-[RuCl (2)(dppm)(2)] to yield [{(dppm)(2) Ru}(2)(O (2) CC (6) H (4) CH (2) OCS (2))](2+) or [{Ru (CH=CHC (6) H (4) Me-4)(CO)(PPh (3))(2)}(2)(O (2) CC (6) H (4) CH (2) OCS (2))], respectively. Electrochemical experiments are also reported in which communication between the metal centres is investigated. |
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