In this article, we report unique reactivities of hydrogensulfide (SH), disulfide (S
2), and oxydisulfide ligands (S
2O
n: n = 1-4) bridging between the Rh—Rh/Ir—Ir bonds. The hydrogensulfide and the disulfide ligand give rise to the S—C and C—C bond formation and the multi C—Cl bond activation, respectively. The oxydisulfide ligand (S
2O
4) shows a photoisomerization resulting in an intriguing crystalline-state photochromism. These reactivities are attributed mainly to the electron-rich Rh—Rh/Ir—Ir bond and the geometrical arrangement and the electronic character of the sulfide ligands.
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