The steric course in the base hydrolysis of some optically active cis -CoCl(en)2(amine)2+ complexes

Fenemor, D. R.; House, Donald A.

doi:10.1016/0022-1902(76)90030-0

Cited by 29 publications

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“…19 The absolute configuration, however, changes in the ligand exchange reactions, since the reaction proceeds through an achiral transition state. [19][20][21][22][23] In this reaction system, an optically active final product was produced from racemic intermediate, indicating the presence of an achiral transition state. We, therefore, postulated that the rate constant for each enantiomer of the final product is independent of the handedness of the intermediate.…”

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confidence: 78%

Mechanism of chiral asymmetry generation by chiral autocatalysis in the preparation of chiral octahedral cobalt complex

1998

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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.

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confidence: 78%