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The reaction of [Ru3(CO)12] with 3,4-dimethyl-1-phenylphosphole under mild conditions affords three derivatives which were identified by means of spectroscopic methods as the substitution compounds [Ru3(CO)12x(PhPC4H2Me2)x ]( x = 1, 2, 3) in which the phosphole ligand acts as a tertiary phosphine bonded through the phosphorus atom. Thermolysis of the monosubstituted [Ru3(CO)11(PhPC4H2Me2)] in cyclohexane affords two new clusters, characterised as [Ru3(CO)9(l 3 :g