Synthesis, Characterization, Electrochemical and Spectroelectrochemical Properties of Ruthenium(II) Complexes Containing Phenylcyanamide Ligands and Effect of the Inner- Sphere on the Ru-NCN Chromophore
Chemistry Department, Sistan and Baluchestan University, P.O. Box 98135-674, Zahedan I. R. IRAN
[Ru(terpy)(bpy)(L)]PF6 complexes, where terpy is 2,2΄:6′,2″– terpyridine, bpy is 2,2΄ - bipyridine and L is monoanions of 4 - bromophenylcyanamide (4 - Brpcyd), 4-methoxyphenylcyanamide (4 - MeOPcyd), 2, 4 - dibromophenylcyanamide (2,4 - Br2pcyd), 2,4-dimethylphenylcyanamide (2,4 - Me2pcyd), 2 - methylphenylcyanamide (2 - MePcyd), phenylcyanamide (Pcyd) and naphtylcyanamide (ncyd) have been prepared and characterized by elemental analysis, IR, 1H-NMR and UV-vis spectroscopies and cyclic voltammetry. Spectroelectrochemistry was used to generate the electronic absorption spectra of the Ru(III) complexes, [Ru(terpy)(bpy)(L)]2+ in acetonitrile solution. The spectral data associated with the Ru(III)-cyanamido LMCT chromophore were compared to those derived from Ru(III) analogues in order to gain a greater understanding the effect of spectator ligands on the nature of the Ru(III)-Cyanamide bond.The data supports greater covalency in the Ru(III)-cyanamide bond of [Ru(terpy)(bpy)(L)]2+ complexes compared to their Ru(III) analogues.