Electrochemistry and spectroelectrochemistry of ruthenium(II)-bipyridine building blocks. Different behaviour of the 2,3- and 2,5-bis(2-pyridyl)pyrazine bridging ligands

We report the results of an investigation, using electrochemical and spectroelectrochemical techniques, into redox properties of uncoordinated free bis-chelating 2,3- and 2,5-bis(2-pyridyl)pyrazine ligands (2,3- and 2,5-dpp) and of the complexes of the [Ru(2,3-dpp)n(bpy)3−n]2+ and [Ru(2,5-dpp)n(bpy)3−n]2+ families (bpy=2,2′-bipyridine), which are used as building blocks for obtaining polynuclear complexes. For comparison purposes, the electrochemical behaviour of the [Ru(2,3-dpp)(DCE-bpy)2]2+complex, where DCE-bpy is 5,5′-dicarboxyethyl-2,2′-bipyridine, has also been investigated. Correlations of the E1/2 values observed for the compounds examined (genetic diagrams) have allowed us to assign all the ligand-based reduction processes as well as to discuss electronic interactions. The localisation of the first three reduction processes for each complex has also been established on the basis of the spectroelectrochemical results. Theoretical calculations (AM1 semiempirical and ab-initio level) carried out for the 2,5-dpp and 2,3-dpp ligands show that, in the uncoordinated state, the former ligand does not exhibit any substantial conformation arrangement, whereas the latter has a stable conformation for a large (56°) dihedral angle between the pyridyl and pyrazine rings. The changes in conformation upon mono- and bis-coordination of 2,3-dpp can account for its peculiar electrochemical behaviour consisting in a change of the number of redox processes with varying coordination state.