Ph3PSe as a convenient synthon for one-step syntheses of Ph3P-substituted selenido carbonyl iron and ruthenium clusters. Crystal structures of Fe3(μ3-Se)(μ-CO)(CO)7(PPh3)2, M3(μ3-Se)2(CO)7(Pph3)2 (MFe or Ru) and Ru4(μ4-Se)2(μ-CO)2(CO)7(PPh3)2

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