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In recent years materials based on aliphatic polyesters (polylactide, polyglycolide and others) have attracted much attention because of the biodegradability and biocompatibility. Ring-opening polymerization (ROP) of lactones initiated by metal complexes is the most common method for the synthesis of such materials due to reproducibility and the ability to control the process. The search for new efficient catalysts of ROP is an actual problem of modern organometallic and macromolecular chemistry. At nowadays an intense investigation of complexes of zinc, aluminum, lanthanides, titanium complexes based on polydentate amines, alkoxides are carried out. In the course of this work we performed investigations on synthesis of new N,N,O-type ligands and aluminum complexes based on them. The structures of all compounds in solution studied by multinuclear NMR spectroscopy (1H, 13C, in some cases 27Al) and in solid phase (X-ray analysis). Complexes obtained demonstrated high activity as initiators for polymerization of lactide.