The formation and stability of the ternary complexes of cadmium(II) with phenanthroline and malonate, phenylmalonate, benzylmalonate, 2-phenylethylmalonate, and 3-phenylpropylmalonate are studied by the potentiometric pH-titration technique in 40% (v/v) dioxane-water at 25°C and 0.1 mol/l ionic strength (NaNO3). In all systems, there are stable ternary complexes. The complexes possess enhanced stability relative to their statistical values. The possible reasons that lead to these results are discussed in terms of π-electron back donation from metal ions to ligands and the intramolecular ligand-ligand aromatic ring stacking interaction. 1H NMR measurements are used to demonstrate the aromatic ring-stacking interaction. The relative contribution of each interactions to the enhanced stability is also estimated. The results show that there are two weak interactions simultaneously observed in these ternary complexes. The interaction strength of aromatic ring stacking in the ternary complexes increases in the phenylalkylmalonate ligand order: L0 < L1 < L2 ≈ L3 (L0 = phenylmalonate, L1 = benzylmalonate, L2 = 2-phenylethylmalonate, L3 = 3-phenylpropylmalonate).
Russian Journal of Coordination Chemistry – Springer Journals
Published: Nov 6, 2006
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