Kinetic Studies on sec ‐Alcohol Racemization with Dicarbonylchloro(pentabenzylcyclopentadienyl)‐ and Dicarbonylchloro(pentaphenylcyclopentadienyl)ruthenium Catalysts

Pentasubstituted cyclopentadienyl complexes of ruthenium R 5 CpRu(CO) 2 Cl (R=Ph, benzyl) form, upon activation with t BuOK, highly active catalysts for racemization of chiral sec ‐alcohols. In combination with suitable resolving enzymes, such catalyst systems can efficiently be utilized for dynamic kinetic resolution reactions providing chiral alcohols, after hydrolysis of the corresponding acetates, in high yields and high enantiomeric purities. Here, three such ruthenium complexes were first characterized by NMR spectroscopy and cyclic voltammetry analysis (CVA) for elucidating their electronic characteristics in detail. Then, accurate kinetic studies were performed providing for the first time the calculated racemization rate constants for such catalyst systems. Furthermore, the dependence of the racemization rate on the electronic structure of the catalyst was investigated from the Hammett constants, substitution patterns of the substrate, and by isotopic labeling studies. The results obtained support the earlier suggested racemization reaction mechanism and indicated that the electron‐rich catalyst Bn 5 CpRu(CO) 2 Cl (Bn=benzyl) racemizes electron‐rich substrates more efficiently and in most cases faster than its pentaphenyl substituted analogue, formerly often considered as the leading catalyst candidate for dynamic kinetic resolution applications. The electron‐deficient catalyst Ph 5 CpRu(CO) 2 Cl, in turn, is more efficient for electron‐poor substrates.