Synthesis, structure, and physicochemical characterizations of a new cationic ruthenium(I)-Ruthenium(I) tetracarbonyl bipyridine dimer precursor for the electrochemical synthesis of an organometallic ruthenium(0) polymer

The synthesis and structure of the Ru(I) dimer [Ru(bpy)(CO)(2)(CH3CN)](2)(PF6)(2) (1; bpy = 2,2 ' -bipyridine) are described. The electrochemical properties of this complex have been examined. The irreversible two-electron reduction of 1 gives [Ru(bpy)(CO)(2)](n), polymer film on the electrode surface, The physicochemical properties of this metal-metal bond based polymer equal those of the polymers formed from the reduction of trans(CH3CN)-[Ru(bpy)(CO)(2)(CH3CN)(2)](2+) or trans(Cl)-[Ru(bpy)(CO)(2)Cl-2] monomer complexes previously described. The Ru(0) polymer can be oxidized in a stepwise manner, leading first to the Ru(I) dimer 1 and then to the Ru(II) monomer 2: cis(CH3CN)-[Ru(bpy)(CO)(2)(CH3CN)(2)](2+). On the other hand, the dimer 1 exhibits an irreversible two-electron oxidation, leading to the same Ru(II) monomer (2), Carbon electrodes modified with the polymer resulting from 1 catalyze the electrochemical reduction of CO2 into CO with a 98% electrical yield at a low potential in hydro-organic or pure aqueous electrolytes.