The reaction of the complexes [P 3 -(P 3 fc 2 )RuCl 2 ], P 3 fc 2 =[η 5 -(R 2 PC 5 H 4 )Fe-η 5 :η 5 -(C 5 H 4 P(R')C 5 H 4 )Fe(η 5 -C 5 H 4 PR 2 )], R, R'=Ph, iPr with linear nitriles results in the formation of the pseudooctahedral complexes, e.g. [P 3 -(P 3 fc 2 )Ru(NCCH 2 R)Cl 2 ], R=H, Ph while the reaction of [(P 3 fc 2 )RuCl 2 ] with pyridines results in partial deligation of one of the ferrocenyl phosphine ligand arms to give the products [P 2 -(η 5 -(R 2 PC 5 H 4 )Fe-η 5 :η 5 -(C 5 H 4 P(R')C 5 H 4 Fe(η 5 -C 5 H 4 PR 2 ))Ru (pyr) 2 Cl 2 ]. The latter products revert to the starting complexes in the absence of excess pyridine in solution. The deligated pendant phosphine may be 'trapped' by reaction with Pd(II) or elemental sulfur. A molecular modelling study has been carried out to verify the conformations of the products. The single crystal structures of mer-[P 3 -(P 3 fc) 2 Ru(CO)Cl 2 ] and mer-[P 2 -(P 3 fc) 2 Ru(pyr) 2 Cl 2 ] have been determined. Cyclic voltammetry supports the role assigned to pyridine in the reaction with the P 3 Fc 2 -RuCl 2 complexes.