Reactivity and X-ray Structural Studies in Ligand Substitution of [Cp/(Ind)-Ru(dppf)Cl] - Epimerisation in [Cp/(Ind)Ru(Josiphos)Cl] {Cp = eta~5-C_5H_5,Ind = eta~5-C_7H_9,dppf = 1,1'-Bis(diphenylphosphanyl)ferrocene,Josiphos =(R)-(-)-1-[(S)-2-(Dipheny

摘要

Ligand substitution of [(Ind)Ru(PPh_3)_2Cl](1)led to the isolation of [(Ind)Ru(PPh_3){Ph_2P(CH_2)_2C_9H_7}Cl](2),[(Ind)Ru-(dppf)Cl](3)and [(Ind)Ru{(Ph_2PCH_2)_3CMe}]PF_6([4]PF_6),and diastereoisomers [(R)- and(S)-(Ind)Ru(Josiphos)Cl] [(R)-5 and(S)-5],where(R)-(S)-Josiphos is the ferrocene-based chi-ral diphosphane ligand(R)-(-)-1-[(S)-2-(diphenylphos-phanyl)ferrocenyl] ethyldicyclohexylphosphane.The Cp analogues of 5,viz.(R)-6 and(S)-6,were also obtained from [CpRu(PPh_3)_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 CH_3CN and NaN_3 in EtOH gave [(Ind)Ru(dppf)(CH_3CN)]PF_6([7]PF_6)and [(Ind)Ru(dppf)(N_3)](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.