The [Cp* IrHCl] 2 dimer reacts under hydrogen with the substituted thiophenes 2- methylthiophene, 2, 5-dimethylthiophene, and 2-acetylthiophene to give ring-opened and hydrogenation μ-thiolate products. Several of these species are formed as diastereomers due to chirality at both the sulfur and the adjacent methine center.