Reactivity Studies of Anticancer Active Dirhodium Complexes with 2-Aminothiophenol

Reactions between the antitumor active compound [Rh2II,II(μ-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 [RhIII(η2-C6H6NS)(η1-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 [Rh2III,III(μ-C6H6NS)2(C6H6NS)2(bpy)2]2+ (3a) as well as [RhIII(C6H6NS)2(bpy)]+ (3b) from reactions of Rh2II,II(μ-O2CCH3)2(bpy)2(CH3CN)2 with 4 equiv of 2-aminothiophenol.