Abstract
Abstract The ion-association constants between the optically active complex cations (A- or Δ-[Si(phen)3]4+) and the resolving agent anions ([Sb2[(+)-tart]2-]2-, tart = tartrate(4-) ion) were determined spectrophotometrically. Ion-association between the complex cation and the eluent union occurred in two steps and the stereoselective interaction was observed in the second step. The second-step association constant for the A-enantiomer (K 2 = 1.41 × 103) is larger than that for the Δ-enantiomer (K 2 = 1.07 × 103). The second-step association plays a dominant role in determining the elution order in column chromatographic resolution. The molecular mechanics calculations for the ion-associated species were performed to obtain information about the microscopic interaction between the ions. The total strain energy for the species containing the A-enantiomer is smaller than that for the Δ-enantiomer and this can explain the experimental finding that the A-enantiomer is eluted faster than the Δ-enantiomer.
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