ИСТИНА

Проект направлен на: 1) Поиск практических альтернатив Pd- и Pt-катализаторам органических реакций на основе недорогих 3d-металлов; 2) Решение фундаментальной проблемы динамических превращений катализаторов в ходе реакций применительно к катализаторам на основе Fe, Co, Ni, Cu; 3) Разработку подходов к созданию гетерогенных катализаторов на основе Ni и Cu методом 3D-печати.

Many carbon-carbon and carbon-heteroatom bond formation reactions proceed with catalysts based on platinum-group metal compounds, both metal complexes and supported (nano)catalysts. One of the most urgent problems in the field is the transition from platinum-group metal compounds to the use of 3d-metal-based catalysts. Fe, Co, Ni, and Cu are much cheaper and often less toxic. At the same time, catalytic processes driven by them are barely predictable. They proceed with dynamic transformations of the catalyst that co-occur in a complex equilibrium, among which are the formation of nanoparticles from metal complexes and salts (deposition), leaching of metal complexes and salts from the nanoparticle surface, oligomerization of monometallic complexes, or poisoning due to the formation, for example, of bimetallic compounds, and reverse deposition of monometallic leaching products on the substrate. Whereas in the case of Pd- and Pt-catalysts dynamic transformations have been relatively studied in recent years, in the case of catalysts based on 3d-metals (Fe, Co, Ni, Cu) systematic studies of dynamic transformations in reactions of carbon-carbon and carbon-heteroatom bond formation are virtually absent, so the project will create a qualitatively new area of research. There has been previously no exact answer to the fundamental question of catalysis in the case of carbon-carbon and carbon-heteroatom bond formation reactions with 3d-metal catalysts. In particular, from the centers observed under catalytic conditions (nanoparticles, mono- and oligomeric metal complexes, products of re-capture of leached metal, or else), what, in fact, provides the observed catalysis? Modern organic synthesis, especially in the production of pharmaceuticals, must meet high standards for reaction efficiency, environmental safety, and purity of the resulting product. Meeting these requirements is possible by developing new highly efficient catalytic systems with deposited nanostructured catalysts. Additive manufacturing technologies offer great opportunities to create new structured heterogeneous catalysts containing catalytically active particles distributed in a polymer matrix. The advantage of additive technologies is the rapid production of catalytic systems optimized for a particular experiment. This project will study the efficiency of distribution of various catalytically active particles in a wide range of polymeric matrices, the availability of active centers of the heterogeneous catalyst for reaction mass molecules under combination reactions, the phenomena of catalyst particles leaching (licking) from polymeric matrices of different nature. We will use theoretical (machine learning, DFT, DFTB, nonclassical molecular dynamics) and experimental methods (ESI-MS, NMR, electron microscopy) to study the reactivity of 3d-metal compounds. The objects of the study will be reactive intermediates in the most actively used cross-coupling and functionalization reactions. Nanostructured 3d-metals, their salts and metal complexes with phosphine, NHC- and other less frequently used ligands were chosen as model catalysts. As organic substrates, we will preferably investigate those with which the unique activity of 3d-metals is manifested. Thus, the project is aimed to: 1) Finding practical alternatives to Pd- and Pt-catalysts for organic reactions based on inexpensive 3d-metals; 2) To solve the fundamental problem of dynamic transformations of catalysts in the course of reactions as applied to catalysts based on Fe, Co, Ni, Cu; 3) Development of approaches to rapid low-scale manufacture heterogeneous catalysts based on Ni and Cu by 3D printing.