Reactivity and X‐ray Structural Studies in Ligand Substitution of [Cp/(Ind)Ru(dppf)Cl] – Epimerisation in [Cp/(Ind)Ru(Josiphos)Cl] {Cp = η 5 ‐C 5 H 5 , Ind = η 5 ‐C 7 H 9 , dppf = 1,1′‐Bis(diphenylphosphanyl)ferrocene, Josiphos = ( R )‐(–)‐1‐[( S )‐2‐(Diphenylphosphanyl)ferrocenyl]ethyldicyclohexylphosphane}

Ligand substitution of [(Ind)Ru(PPh 3 ) 2 Cl] ( 1 ) led to the isolation of [(Ind)Ru(PPh 3 ){Ph 2 P(CH 2 ) 2 C 9 H 7 }Cl] ( 2 ), [(Ind)Ru(dppf)Cl] ( 3 ) and [(Ind)Ru{(Ph 2 PCH 2 ) 3 CMe}]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 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(PPh 3 ) 2 Cl] ( 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 3 CN and NaN 3 in EtOH gave [(Ind)Ru(dppf)(CH 3 CN)]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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)