Bimetallic complexes based on carboxylate and xanthate ligands: synthesis and electrochemical investigations.

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.

Multimetallic arrays: symmetrical bi-, tri- and tetrametallic complexes based on the group 10 metals and the functionalisation of gold nanoparticles with nickel-phosphine surface units.

Homobimetallic complexes of nickel, palladium and platinum, [(L2M)2(S2CNC4H8NCS2)]2+, are formed on reaction of the piperazine bis(dithiocarbamate) linker, KS2CNC4H8NCS2K, with [MCl2L2] (M=Ni, L2=dppe, dppf; M=Pd, L2=dppf; M=Pt, L=PEt3, PMePh2, PPh3, L2=dppf). [{Pd(C,N-C6H4CH2NMe2)}2(S2CNC4H8NCS2)] can be obtained in the same way. On reaction of [MCl2L2] (M=Pd, Pt) with the zwitterion S2CNC4H8NH2, a symmetrisation process occurs to yield a mixture of the complexes [M(S2CNC4H8NH2)L2]2+ and [(L2M)2(S2CNC4H8NCS2)]2+. However, the monometallic complexes [L2Ni(S2CNC4H8NH2)]2+ (L2=dppe, dppf) and [(L2Ni)2(S2CNC4H8NCS2)]2+ can be prepared without ready symmetrisation. Starting from the previously reported [(dppm)Ru(S2CNC4H8NH2)]2+, the heterotrimetallic products [(dppm)Ru(S2CNC4H8NCS2)M(dppf)]2+ (M=Pd, Pt) can be prepared without symmetrisation occurring. The crystal structures of five complexes are reported. The metalla-dithiocarbamate complexes [L2Ni(S2CNC4H8NCS2)] (L2=dppe, dppf) were used to functionalise the surface of gold nanoparticles by the displacement of a citrate shell to yield NiAu and FeNiAu materials.