The chiral complexes CpRu(LL*)PPh 3 , Cp=η 5 -C 5 H 5 , LL*-1=anion of 2-N-[(S)-l-phenylethyl]pyrrolecarbaldimine (1a/1b), LL*-2=anion of 2-N-[(R)-hydroxybut-2-yl)]pyrrolecarbaldimine (2a/2b) and LL*-3=anion of N-[(S)-1-phenylethyl]salicylaldimine (3a/3b), can be prepared by reaction of CpRu(PPh 3 ) 2 Cl and the corresponding ligand HLL* in boiling toluene. An X-ray structure analysis of diastereomerically pure 1a shows S Ru configuration. The phenyl substituent of the ligand adopts a T-shape arrangement with respect to the Cp ring. The PPh 3 ligand is in a right handed propeller conformation. The activation parameters of the epimerization 1a⇌1b were determined to be ΔH ≠ =(133±33) kJmol −1 and ΔS ≠ =(77±26) JK −1 mol −1 . The equilibrium ratios are 1a:1b=86:14, 2a:2b=1:1 and 3a:3b=88:12, the attractive interaction between the Cp ring and the phenyl substituent of the chiral center in the chelating ligand LL* favoring one diastereomer of the complexes 1a/1b and 3a/3b.