Abstract

The electrochemical behavior of binuclear ruthenium(II) complexes of the type [{(arene)RuCl2}2] where arene = benzene (1), toluene (2), p-cymene (3) and hexamethylbenzene, (HMB) (4), have been studied by cyclic voltammetry, coulometry and voltammetry with rotating disk and ring-disk electrodes. These compounds undergo electrochemical quasi-reversible reduction in dimethylsulphoxide (DMSO) and acetonitrile (MeCN). The ruthenium(I) species formed react in a very fast chemical reaction (EC mechanisms), although the rate constants of electrochemical and chemical processes are different for the arenes studied. Conditional rate constants (k) and charge transfer coefficients (?) for the cathodic reactions were determined by rotating disk techniques, and the kinetic collection efficiency (Nk) was determined with a rotating ring-disk electrode. On the other hand, the binuclear complexes 1 and 2 are quasi-reversibly oxidized in MeCN solution in two electron steps yielding binuclear Ru(III) species, while complex 3 is partially oxidized to give a mixture of products, and complex 4 generates a very unstable species, which chemically returns to the starting reduced complex.