Pyrolysis of {Ru 3 (μ-dppm)(CO) 9 } n (dppa) (n = 1 or 2) afforded Ru 3 (μ 3 -PPhCH 2 PPh 2 )(μ 3 -η 1 :η 2 :P-C 2 PPh 2 )(μ-PPh 2 )(Ph)(CO) 6 , containing an Ru 3 chain bridged by a dephenylated dppm ligand and by C 2 PPh 2 and PPh 2 ligands derived from the dppa ligand. The phenyl group from the dppm ligand has been trapped by one of the Ru atoms to give a rare example of a cluster-bound σ-Ph group. The molecular structure of Ru 3 (μ-H){μ 3 -η 1 ,η 2 -CCHP(O)Ph 2 }(μ-PPh 2 )(μ-dppm) (CO) 6 , obtained on one occasion from the mono-cluster complex, is also described.