Аннотация:In organometallic chemistry the structure of the organic ligand determines the structure and properties of the whole molecule. The last results of our scientific group on application of novel polydentate ligands with O-, N-, S-coordinating atoms to the synthesis of main group (Ge, Sn; Al) and transition metal (Ti) complexes will be reported. A number of these complexes were used as ligands for Pd, Mo, W derivatives, as catalysts in cross-coupling reactions, as initiators in ring-opening polymerization (ROP) of lactones. The strategy to the synthesis of macromonomers using modified Al complexes will be also presented.