Reactivity and X-ray structural studies in ligand substitution of [Cp/(Ind)-Ru(dppf)Cl] - Epimerisation in [Cp/(Ind)Ru(Josiphos)Cl] {Cp = η⁵-C₅H₅, Ind = η⁵-C ₇H₉, dppf = 1,1′-bis(diphenylphosphanyl)ferrocene, Josiphos = (R)-(-)-1-[(S)-2-(diphenylphosphanyl)ferrocenyl] ethyldicyclohexylphosphane}

Ligand substitution of [(Ind)Ru(PPh₃)₂Cl] (1) led to the isolation of [(Ind)Ru(PPh₃)(Ph₂P(CH₂) ₂C₉H₇}Cl] (2), [(Ind)Ru(dppf)Cl] (3) and [(Ind)Ru{(Ph₂PCH₂)₃CMe}]PF₆ ([4]PF₆), and diastereoisomers [(R)- and (S)-(Ind)Ru(Josiphos)Cl] [(R)-5 and (S)-5], where (R)-(S)-Josiphos is the ferrocene-based chiral diphosphane ligand (R)-(-)-1-[(S)-2-(diphenylphosphanyl)ferrocenyl] ethyldicyclohexylphosphane. The Cp analogues of 5, viz. (R)-6 and (S)-6, were also obtained from [CpRu(PPh₃)₂Cl] (1a). Josiphos-dependent epimerisation was observed, with conversion of the (S) isomer to the (R) isomer in both cases. Chloride abstraction of 3 with NaPF ₆ in CH₃CN and NaN₃ in EtOH gave [(Ind)Ru(dppf)(CH₃CN)]PF₆ ([7]PF₆) and [(Ind)Ru(dppf)(N₃)] (8), respectively. The azido ligand in 8 underwent [3+2] dipolar cycloaddition with dimethyl acetylenedicarboxylate to give a N-bound bis-(methoxycarbonyl)-1,2,3-triazolato complex, 9. X-ray crystal structures of the new complexes, except (R)-5, (S)-5 and (S)-6, have been determined.