Synthesis, Characterization, Electrochemical and Spectroelectrochemical Properties of Ruthenium(II) Complexes Containing Phenylcyanamide Ligands and Effect of the Inner- Sphere on the Ru-NCN Chromophore

[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), 4methoxyphenylcyanamide (4 MeOPcyd), 2, 4 dibromophenylcyanamide (2,4 Br2pcyd), 2,4dimethylphenylcyanamide (2,4 Me2pcyd), 2 methylphenylcyanamide (2 MePcyd), phenylcyanamide (Pcyd) and naphtylcyanamide (ncyd) have been prepared and characterized by elemental analysis, IR, H-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)] 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)] complexes compared to their Ru(III) analogues.