Crystal structures of [Rh(η5-C5H5)(C3S5)] and [Rh(η5-C5Me5)(C3S5)]2 and properties of their oxidized species

[Rh(η5-C5H5)(C3S5)] and [Rh(η5-C5Me5)(C3S5)]2 [C3S52−=4,5-disulfanyl-1,3-dithiole-2-thionate(2-)] were prepared by reactions of [NMe4]2[C3S5] with [Rh(η5-C5H5)Cl2]2 and [Rh(η5-C5Me5)Cl2]2, respectively. Their X-ray crystal structural analyses revealed a monomeric form for the former complex and a dimeric geometry containing bridging S–Rh–S bonds for the latter in the solid state. They were reacted with bromine to afford [RhBr(L)(C3S5)] (L=η5-C5H5 and η5-C5Me5) with the Rh–Br bond and one electron-oxidation on the C3S5 ligand. ESR spectra and spin densities for these oxidized species are discussed.