[1,1'-Bis(di-phenyl-phosphan-yl)cobalto-cenium-κ(2) P,P'](η(5)-cyclo-penta-dien-yl){2-[4-(4-ethynylphen-yl)phen-yl]ethynyl-κC}ruthenium(II) hexa-fluorido-phosphate.

In the title compound, [CoRu(C5H5)(C16H9)(C17H14P)2]PF6, the Ru(II) atom is coordinated by a cyclo-penta-dienyl ring in an η(5)-mode, one C atom from a 4,4'-diethynyl-1,1'-biphenyl ligand and two P atoms from a chelating 1,1'-bis-(di-phenyl-phosphan-yl)cobaltocenium ligand, giving a three-legged piano-stool geometry. In the crystal, weak C-H⋯F hydrogen bonds link the complex cations and hexa-fluorido-phosphate anions into a three-dimensional supra-molecular structure.

Bimetallic ruthenium complexes bridged by divinylphenylene bearing oligo(ethylene glycol)methylether: synthesis, (spectro)electrochemistry and the lithium cation effect.

A series of 1,4-disubstituted ruthenium-vinyl complexes, (E,E)-[{(PMe3)3(CO)ClRu}2(µ-HC=CH-Ar-CH=CH)], in which the 1,4-diethenylphenylene bridge bears two oligo(ethylene glycol)methyl ether side chains at different positions (2,5- and 2,3-positions), were prepared. The respective products were characterized by elemental analyses and NMR spectroscopy. The structures of complexes 1b and 1e were established by X-ray crystallography. The electronic properties of the complexes were investigated by cyclic voltammetry, and IR and UV-vis/NIR spectroscopies. Electrochemical studies showed that the 2,5-substituents better stabilized the mixed-valence states; the electrochemical behavior was greatly affected by lithium cations, especially complex 1g with 2,3-substituents, which was further supported by IR and UV-vis/NIR spectra changes. Spectroelectrochemical studies showed that the redox chemistry was dominated by the non-innocent character of the bridging fragment.