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), 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, 1-nmr and uv-vis spectroscopies and cyclic voltammetry. spectro electro chemistry 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.