Pavlenko V. Polynuclear coordination compounds of transition 3d-metals based on simple and chelating pyrazoles

The dissertation is devoted to the development of synthetic approaches for obtaining pyrazole - containing ligand systems of different types and complex compounds and coordination polymers of 3d metals on their basis, research of processes of complexation of pyrazole - containing ligands with metal ions in solutions, establishment of structure of synthesized compounds. catalytic activity of model complexes in hydrolysis and oxidation reactions of biologically important substrates and pesticides, as well as electrocatalytic activity of thermolysis products of copper- containing pyrazolate complexes in the reaction of electrochemical reduction of oxygen. On the example of the system "copper-pyrazole-containing ligand" it is determined that when using the same components of the starting reagents by different methods of synthesis (electrochemical, conventional and oxidative dissolution method) compounds of different nuclearity are formed. Physicochemical and spectral properties of the extracted compounds have been studied. The results of the study of catalytic reactions of hydrolysis of the pesticide paraoxon-ethyl (POE) and intramolecular transesterification of activated phosphodiester - a synthetic analogue of RNA 2-(oxypropyl)-n-nitrophenylphosphate (HPNP) in the presence of PN-based P II) and it is shown that the course of reactions follows the Michaelis-Menten model; the calculated kinetic parameters kobs (pseudofirst order hydrolysis rate constant), KM (Michaelis constant), kcat (number of revolutions) and kcat / KM indicate high efficiency of complexes as catalysts in these reactions; the complex-substrate interaction is a truly catalytic act, because more than one molecule of the substrate is cleaved by one molecule of the complex. The mechanism of cooperative action of metal centers in hydrolysis reactions catalyzed by zinc hydrolases is proposed The possibility of using the complexes Cu(OAc)2(Hdmpz)2, Cu2(OAc)4(Hdmpz)2, Cu11(dmpz)10(OAc)6(OH)6(H2O)2, Cu11(dmpz)10(OAc)6(OH)6(DMSO)6 and [Cu3(dmpz)3(DMF)4(OAc)(OH)(H2O)][Cu3(dmpz)3(DMF)(NCS)3(OH)] of different composition and nuclear power as a precursor for the creation of electrocatalysts for oxygen reduction showed that the use of a mononuclear complex for this purpose was more effective than the use of multinuclear complexes