Complexes in the series Ru(OEP)(RR’S)(2) and Ru(OEP)(RR’SO)(2) (where OEP = the dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin, R = methyl, ethyl, or decyl, and R’ = methyl or ethyl) were prepared by treatment of the dimer [Ru(OEP)](2) with the appropriate thioether or sulfoxide ligands. Similarly, complexes of the type [Ru(OEP)(RR’S)(2)][BF4] and [Me(4)N][Ru(OEP)(PhCOO)(2)] were prepared by the addition of the appropriate thioether or [Me(4)N][PhCOO] to the dimer [Ru(OEP)](2)[BF4](2). All the complexes were characterized by use of H-1-NMR, IR, and UV/vis spectroscopy, cyclic voltammetry (CV), and elemental analysis. IR data show that the Ru(OEP)(RR’SO)(2) complexes exist as the bis(S-bound) isomers in the solid state; CV data suggest that in solution rearrangement of S-bound to O-bound sulfoxide occurs after a metal-centered oxidation. The crystal structure of [Ru(OEP)(decMs)(2)][BF4] (decMS = n-decyl methyl sulfide) was obtained; the crystals are triclinic, P ($) over bar 1, with a = 10.995(4) Angstrom, b = 13.843(3) Angstrom, C = 10.305(4) Angstrom, alpha = 101.60(2)degrees, beta = 97.46(3)degrees, gamma = 86.82(3)degrees, and Z = 1. The structure was solved by the Patterson method and was refined by full-matrix least-squares procedures to R = 0.050 and R(W) = 0.040 for 2948 reflections with I greater than or equal to 3 sigma(I). The solid state geometry of [Ru(OEP)(decMS)(2)][BF4]is not significantly different from that previously found for Ru(OEP)(decMS)(2).