ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The 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 ΔΔHΔ-Λ# values being largely compensated by the ΔΔSΔ-Λ# 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.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19900730214
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