Disulfide-bridged dinuclear ruthenium complexes [(Ru(MeCN)(P(OMe)(3))(2)}(2)(mu -X)(mu,eta (2)-S-2)][ZnX3 = Cl (2), Br (4)), [{Ru(MeCN)(P(OMe)(3))(2)}(2)(mu -Cl)(2)(mu,eta (1)-S-2)1](CF3SO3) (5), [{Ru(MeCN)( P(OMe)(3))(2)}(2)(mu -Cl)-(mu,eta (2)-S-2)](BF4) (6), and [{Ru(MeCN)(2)(P(OMe)(3))(2)}(mu -Cl)(mu,eta (1)-S-2)](CF3SO3)(3) (7) were synthesized, and the crystal structures of 2 and 4 were determined. Crystal data: 2, triclinic, P1, a = 15,921(4) Angstrom, b= 17.484(4) Angstrom, c = 8.774(2) Angstrom, alpha = 103.30(2)degrees, gamma = 109.68(2)degrees, V = 2124(1) Angstrom (3), Z = 2, R (R-w) = 0.055 (0.074); 4, triclinic, P1, a = 15.943(4) Angstrom, b = 17.703(4) Angstrom, c = 8.883(1) Angstrom, alpha = 102.96(2)degrees, beta = 102.02(2)degrees, gamma = 109.10(2)degrees, V = 2198.4(9) Angstrom3, Z = 2, R (R-w) = 0.048 (0.067). Complexes 2 and 4 were obtained by reduction of the disulfide-bridged ruthenium complexes [{RuX(P(OMe)(3))(2)}(mu -X)(2))] (X = Cl (1), Br (3)) with zinc, respectively. Complex 5 was synthesized by oxidation of 2 with AgCF3SO3. Through these redox steps, the coordination mode of the disulfide ligand was converted from mu,eta (1) in 1 and 3 to mu,eta (2) in 2 and 4 and further reverted to mu,eta (1) in 5. Electrochemical studies of 6 indicated that similar conversion of the coordination mode occurs also in electrochemical redox reactions.