Conditions for chiral asymmetry generation in the preparation of the chiral octahedral cobalt complex

We have reported that the random chiral asymmetry generation, which is a spontaneous preferential generation of one enantiomer, was observed in the synthesis of a chiral octahedral cobalt complex, cis‐[CoBr(NH3)(en)2]Br2. In this article, we review our studies to explain in this system the autocatal...

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Veröffentlicht in:Chirality (New York, N.Y.) N.Y.), 2001, Vol.13 (8), p.435-440
Hauptverfasser: Asakura, Kouichi, Osanai, Shuichi, Kondepudi, Dilip K.
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Sprache:eng
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Zusammenfassung:We have reported that the random chiral asymmetry generation, which is a spontaneous preferential generation of one enantiomer, was observed in the synthesis of a chiral octahedral cobalt complex, cis‐[CoBr(NH3)(en)2]Br2. In this article, we review our studies to explain in this system the autocatalytic growth of small enantiomeric excess that arises due to statistical fluctuations. One important experimental finding was that the rate of chiral autocatalysis increased with increasing the degree of supersaturation. Furthermore, our numerical simulation indicates that even small inhomogeneities in the reaction system may play a significant role because their effect is amplified by the autocatalytic reaction under appropriate conditions. In a small volume, fluctuations in concentration can grow if the autocatalytic growth overcomes the diffusional loss of the excess concentration from this volume. This may makes the enantiomeric excess of the chiral complex randomly fluctuate from run to run. Chirality 13:435–440, 2001. © 2001 Wiley‐Liss, Inc.
ISSN:0899-0042
1520-636X
DOI:10.1002/chir.1058