Photoassisted synthesis of mixed-metal clusters: [PPN] [CoOs3(CO)13], H2RuOs3(CO)13, and H2FeOs3(CO)13

The utility of photochemical methods for the directed synthesis of mixed-metal metal clusters has been explored. The 366 nm photolysis of a solution containing PPN] Co(CO)₄] (PPN = (Ph₃P)₂N⁺) and Os₃(CO)₁₂ gives the new cluster PPN]CoOs₃(CO)₁₃] in 33% yield. Irradiation of a mixture of Fe(CO)₅ and H₂Os₃(CO)₁₀ yields H₂FeOs₃(CO)₁₃ in 95% yield, and photolysis of Ru₃(CO)₁₂ in the presence of H₂Os₃(CO)₁₀ gives the new cluster H₂RuOs₃(CO)₁₃. Details of these syntheses, their probable mechanisms, and the characterization of the new compounds are discussed.