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At present time materials based on biodegradable polymers (polylactide, poly-ε-caprolactone etc.) attract considerable attention of researchers. The main method of synthesis of these compounds is the polymerization of cyclic esters (lactide, glycolide, ε-caprolactone), which runs with the ring opening. The metal complexes based on polydentate ligands are widely used as initiators of this process. In the course of this work, complexes of zinc, aluminum and titanium based on substituted dialkanolamines, diethylenetriamine and related ligands have been synthesized. The structures of the compounds were investigated by multinuclear NMR spectroscopy and, in some cases, by X-ray analysis. Some of the complexes demonstrated a moderate catalytic activity in the polymerization of lactide.