The effect on chromatographic behavior, on thin layers of silica gel, of the electronegativity of ligator atoms has been studied for three series of β-diketonato complexes of the type [M(acac)
], and [M(acac)
] (where M represents cobalt(III), chromium(III) or ruthenium(III), acac is the 2,4-pentanedionato ion, phacphac is the 1,3-diphenyl-1,3-propanedionato ion, phacphSac is 3-mercapto-1,3-diphenyl-prop-2-en-1-one, phSacphSac is the 3-mercapto-1,3-diphenyl-prop-2-en-1-tion ion, and
= 0–3). For chromatographic separations, ten typical normal-phase mobile phases were used, five mono-component and five two-component. For all the complexes examined it was found that substitution of the donor oxygen atom by a less electronegative sulfur atom resulted in increased mobility of the complex. It was also established that substitution of the acac ligand resulted in increased
values. For all the complexes examined a linear dependence was observed between the
values of the complexes and the number of acac ligands substituted by phSacphSac ligands. On the basis of these results, possible separation mechanisms are discussed.
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