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Mechanism of chiral asymmetry generation by chiral autocatalysis in the preparation of chiral octahedral cobalt complex
Authors:Kouichi Asakura  Dilip K Kondepudi  Reesheda Martin
Abstract:Chiral asymmetry generation, the predominant production of one enantiomer in a non-chiral environment, could occur in the production of the chiral complex cis-CoBr(NH3)(en)2]Br2 by the reaction of Co(H2O)2{(OH)2Co(en)2}2](SO4)2 with ammonium bromide in an aqueous medium. The main kinetic steps in the reaction system have been determined. During the reaction, the product crystallizes at an early stage. When a very small amount of crystalline enantiomer was added to the reaction system at an early stage, the same enantiomer was produced preferentially; in addition, the enantiomeric excess of the product increased with increasing the stirring rate. Thus, it seems that each enantiomer generates chiral crystals that could self-replicate through secondary nucleation when the solution is stirred; these crystals in turn enhance the production of the same enantiomer. With a computer code that simulates such a kinetic mechanism, it is shown that enantiomeric excess observed in the experiments could be reproduced. Chirality 10:343–348, 1998. © 1998 Wiley-Liss, Inc.
Keywords:chiral asymmetry generation  chiral autocatalysis  primary nucleation  secondary nucleation  chiral cobalt complex
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