Iridium Insertion to Triosmium Cluster Containing Unsaturated Os–Os Bonds

Treatment of the triosmium hydrido cluster, [Os3(μ-H)2(CO)10], with one equivalent of [IrCp*Cl2]2 (Cp* = pentamethylcyclopentadiene) in refluxing THF afforded four osmium–iridium clusters, including [Os3Ir2(μ-CO)(μ-H)2(CO)9(Cp*)2] (1), [Os3IrCp*(μ-H)3(μ-Cl)(CO)9] (2), [Os3IrCp*(μ-H)(μ-Cl)(μ-CO)(CO)9] (3) and [Os2IrCp*(μ-H)(μ-Cl)(CO)7] (4), in moderate yields. The reactivity of complex 3 with hydrogen, carbon monoxide, and thallium hexafluorophosphate was studied. Complex 4 was found to react with [Os3(μ-H)2(CO)10] to give 2 and 3. All of the new compounds were characterized by conventional spectroscopic methods and single-crystal X-ray analysis.