Abstract

AbstractThe kinetics of the electron transfer between reduced spinach [2Fe‐2S]‐ferredoxin and the optically active complexes [Co((R,R)‐ or (S,S)‐alamp)py]+ (I), [Co((R,R)‐ or (S,S)‐promp)H2O]+ (IIa), and [Co((R,R)‐ or (S,S)‐promp)py]+ (IIb) have been investigated. The reactions are stereoselective, and for I and IIa, the Stereoselectivity strongly depends on temperature due to large differences in the activation enthalpy between enantiomeric reagents. Isokinetic behaviour is observed between enantiomers, the ΔΔH values being largely compensated by the ΔΔS values. The compensation behaviour is explained by the combination of stereochemical interactions and desolvation processes on formation of the precursor complex or the transition state.

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