• Analytical Science and Technology
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• v.6 no.1
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• pp.107-119
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• 1993

The purpose of this study is to investigated the elution behavior of platinoid metal acetylacetonates, which is the key to elucidate their retention mechanism and optimize their RPLC separation conditions. The retention data of four platinoid metal acetylacetonates have been measured on four different columns in methanol-water and acetonitrile-water systems. The retention of uncharged platinoid metal acetylacetonates is interpreted by solvophobic effect. The retention of platinoid metal acetylacetonates is also greatly influenced by the geometric structure of the complexes. The square planar chelates, $Pd(acac)_2$, $Pt(acac)_2$, are retained longer than the octahedral chelates, $Rh(acac)_3$, $Ir(acac)_3$. It is likely due to that square planar chelates show greater interaction with nonpolar stationary phase than octahedral chelates. The results of van't Hoff plots have shown that platinoid metal acetylacetonates is operated on the same retention mechanism in the temperature range of $25{\sim}45^{\circ}C$. The study of the retention mechanism by the enthalpy-entropy compensation phenomenon has indicated that the retention mechanism of octahedral chelates and square planar chelates do not vary with the composition change of methanol-water mobile phase, respectively. In acetonitrile-water mobile phase, however, the retention mechanism is observed to be more complicated. Optimum condition for the separation of four platinoid metal acetylacetonates is found to be 40% methanol, polymeric C18 column, and $45^{\circ}C$.