The complexes trans-[Ru(py)(4)L-2] where py = pyridine and L = (2-chlorophenyl)-, (2,3-dichlorophenyl)-, (2,4,5-trichlorophenyl)-, (2,3,4,5-tetrachlorophenyl)- and (pentachlorophenyl)cyanamide were synthesized and characterized by electronic and H-1 NMR spectroscopies. A crystal structure of trans-[Ru(py)4((2-chlorophenyl)cyanamide)(2)] showed the expected trans coordination of the phenylcyanamide ligands. Crystal structure data: space group C2/c, with a, b, and c = 40.6441(3), 9.2003(1), and 22.6946(2) Angstrom, respectively, beta = 116.387(1)degrees, V = 7602.2(1) Angstrom(3), and Z = 8. The structure was refined by using 4943 independent reflections with I > 2 sigma(I) to a final R factor of 0.060. Spectroelectrochemistry was used to generate the electronic absorption spectra of the Ru(III) complexes trans-[Ru(py)(4)L-2](+). Ru(III)-cyanamidle coupling elements derived from charge transfer spectral data of the trans-[Ru(NH3)(5)L](2+) complexes were significantly larger than those of the corresponding [Ru(NH3)(5)L](2+) complexes.