Reactions between the antitumor active compound [Rh-2(II,II)(mu-O2CCH3)(2)(phen)(2)(CH3CN)(2)][PF6](2) (phen = 1,10-phenanthroline) and excess 2-aminothiophenol in the presence of oxygen yields the neutral complex [Rh-III(eta(2)-C6H6NS)(eta(1)-C6H6NS)(2)(phen)] (2), which was characterized by spectroscopic and crystallographic methods. Dinuclear intermediates are most likely involved in this chemistry as indicated by the isolation of [Rh-2(III,III)(mu-C6H6NS)(2)(C6H6NS)(2)(bPY)(2)](2+) (3a) as well as [Rh-III(C6H6NS)(2)(bpy)](+) (3b) from reactions of Rh-2(II,II)(mu-O2CCH3)(2)(bpy)(2)(CH3CN)(2) with 4 equiv of 2-aminothiophenol.