Formation of a Novel μ‐Nonasulfido Ligand and Its Degradation into a μ‐Disulfido Ligand at a Diiridium Center

Surprisingly, nine sulfur atoms are present in the bridging polysulfido ligand in the diiridium complex 1 (shown on the right), which was prepared by the reaction of 2 with S8. Upon treatment with NaBPh4, the nonasulfido ligand in 1 is converted into a bridging disulfido ligand, and this reaction is accompanied by a one-electron oxidation of the diiridium core to give the paramagnetic diiridium cation 3. Cp* = C5Me5.