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The creation of new organic ligands capable of stabilizing unusual valence states and the coordination polyhedra of metal atoms is one of the directions of organometallic chemistry. Such metal complexes are increasingly used in the field of organic chemistry as metal complex catalysis of organic reactions. One of these important classes of compounds are the derivatives of divalent metal of Group 14 (germanium and tin). In the chemistry of these derivatives, the design of ligand systems turns out to be extremely important, as it allows stabilizing the electron-deficient structures. Germylenes and stannylenes, possessing a singlet structure (the presence of a lone electron pair), can be convenient ligands (σ-donors) for the transition metal complexes and can be use in catalysis, for example, as initiators for ring opening polymerization of cyclic esters (ROP). Another important class of compounds of non-transition elements are complexes of zinc, aluminum and gallium. The interest in these derivatives has recently increased many times due to the fact that they are one of the most promising catalysts for the ring opening polymerization of cyclic esters and for the reaction of CO2 insertion in the C–O bond in substituted oxiranes. Extremely important is the type of catalyst, which determines the structure and properties of the resulting polymers. Therefore, it is of interest to synthesize new derivatives of zinc, aluminum, gallium based on ligands, which make it possible to vary the Lewis acidity of the central atom and stabilize the geometry of the molecule that is convenient for application in catalysis.