Ruthenium terpyridine complexes containing a pyrrole-tagged 2,2'-dipyridylamine ligand-synthesis, crystal structure, and electrochemistry

Ruthenium(II) terpyridine complexes containing the pyrrole-tagged 2,2'-dipyridylamine ligand PPP (where PPP stands for N-(3-bis(2-pyridyl)aminopropyl)pyrrole with the general formula Ru(tpy)(PPP)X](n+) (1, X = Cl(-); 2, X = H(2)O; 3, X = CH(3)CN; tpy = 2,2':6',2"-terpyridine) have been synthesized and characterized by (1)H NMR, IR, UV-vis, mass spectrometry, and elemental analysis. 1 and 2 have been structurally characterized by X-ray crystallography. Both 1 and 2 were successfully immobilized onto glassy carbon electrode via anodic oxidation of the pyrrole moiety on the PPP ligand to give stable and highly electroactive polymer films. Cyclic voltammetric studies of 1 in acetonitrile revealed a Ru(III)/Ru(II) couple at 0.4 V vs Cp(2)Fe(+/0) initially, but another redox couple resulting from chloride substitution by acetonitrile developed at E(1/2) = 0.82 V upon repetitive potential scan. This ligand substitution was induced by the acidic local environment caused by the release of protons during pyrrole polymerization. The electropolymerization of 2 in aqueous medium allowed the observation of the formation of Ru(IV)═O species in polypyrrole film. As the film grew thicker, the size of the Ru(III)/(/)Ru(II) couple (E(1/2) = 0.8 V vs SCE at pH 1) of polyRu(tpy)(PPP)(OH(2))](n+) increased accordingly, whereas the growth of the Ru(IV)/Ru(III) couple (E(1/2) = 0.89 V vs SCE at pH 1) leveled off after the film had reached a certain thickness. The Pourbaix diagram of the E(1/2) of the Ru(III) /Ru(II) and Ru(IV)/Ru(III) couples vs pH of the electrolyte medium has been obtained. The resulting polyRu(tpy)(PPP)(OH(2))](n+) film is electrocatalytically active toward the oxidation of benzyl alcohol.