Reactions of [Cp ∗RuCl(μ-SR) 2RuCp ∗Cl] ( 2; Cp ∗ = η 5- C 5 Me 5) with Li 2S 2 in toluene at room temperature afforded then diruthenium complexes bridged by one disulfide and two thiolate ligands [Cp ∗Ru(μ-S 2)(μ-SR) 2RuCp ∗] ( 3a, R = Pr i, 3b, R = PhCH 2), whose structures have been determined by X-ray crystallography. Crystal data for 3a: tetragonal, space group P4 12 12 (No. 92), a = 15.368(5), c = 25.863(8) A ̊ , V = 6108(4) A ̊ 3, Z = 8, and R(Rw) = 0.055 (0.066) for 2582 reflections (| F 0| >; 3 θ( F 0)). 3b: monoclinic, space group P2 1/ n (No. 14), a = 10.607(1), b = 23.214(3), c = 14.107(3) A ̊ , β = 90.56(1)°, V = 3437(1) A ̊ 3, Z = 4, and R(Rw) = 0.067 (0.074) for 5744 reflections (| F 0| >; 3 θ( F 0)). Cyclic voltammograms of 3 each exhibit two consecutive oxidation waves and one reduc that are all reversible.