Isolation of the Novel Dirhodium(II/II) Thiolate Compound Rh<sub>2</sub>(η<sup>1</sup>-C<sub>6</sub>H<sub>5</sub>S)<sub>2</sub>(μ-C<sub>6</sub>H<sub>5</sub>S)<sub>2</sub>(bpy)<sub>2</sub>
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The reaction of the anticancer active compound [Rh2(μ-O2CCH3)2(bpy)2(CH3CN)2][BF4]2 (1) (bpy = 2,2‘-bipyridine) with NaC6H5S under anaerobic conditions yields Rh2(η1-C6H5S)2(μ-C6H5S)2(bpy)2·CH3OH (2), which was characterized by UV−visible, IR, and 1H NMR spectroscopies as well as single-crystal X-ray crystallography. Compound 2 crystallizes as dark red platelets in the monoclinic space group C2/c with cell parameters a = 20.398(4) Å, b = 11.861(2) Å, c = 17.417(4) Å, β = 108.98°, V = 3984.9(14) Å3, Z = 4. The main structural features are the presence of a [Rh2]4+ core with a Rh−Rh distance of 2.549(2) Å bridged by two benzene thiolate ligands in a butterfly-type arrangement. The axial positions of the [Rh2]4+ core are occupied by two terminal benzene thiolates. Cyclic voltammetric studies of 2 reveal that the compound exhibits an irreversible oxidation at +0.046 V in CH3CN, which is in accord with the fact that the compound readily oxidizes in the presence of O2. The fact that this unusual dirhodium(II/II) thiolate compound is formed under these conditions is an important first step in understanding the metabolism of dirhodium anticancer active compounds with thiol-containing peptides and proteins.
