Isu - quantumandcatchem quantumandcatchem

Establishing of fundamental aspects of prospective Suzuki-Miyaura reaction with available non-reactive substrates using novel kinetic investigation methods

Grant of Russian Science Foundation No.19-13-00051

The investigation of palladium-catalyzed cross-coupling reactions using different nucleophiles catalyzed by transition metal compounds is one of the most urgent issues of chemical science in the joint field of organic synthesis and catalysis. An empirical search of the reaction conditions and catalytic systems is much more ineffective in comparison with the rational approach based on knowledge about fundamental peculiarities of the reaction proceeding. Therefore, we aimed to carry out the comprehensive kinetic study of the coupling of aryl halides with aryl boronic compounds known as Suzuki-Miyaura reaction using available but nonreactive aryl chlorides and ‘ligand-free’ Pd catalytic systems (i.e., those do not contain additives of air- and moisture-sensitive and simultaneously expensive and toxic or dangerously explosive phosphorous- and nitrogen-containing ligands). The main results of the project will be the novel fundamental knowledge about the mechanism of catalysis in the Suzuki-Miyaura reaction using available but nonreactive aryl chlorides with ‘ligand-free’ catalytic systems being the most prominent from practical view. In particular, the type of catalysis mechanism (homogeneous, nanosized or heterogeneous) as well as the mechanisms of active species formation and deactivation (including their coupling with the main catalytic cycle) will be established. Additionally, important data (including that of practical view) regarding the nature of the fast, reversible, rate- and selectivity-determining steps will be obtained. The results obtained will possess high practical significance due to fundamental data about catalysis mechanism of the reaction under consideration will allow developing of effective catalytic systems for practical application of the process in organic synthesis of the valuable drugs and agrochemicals.

Experimental and Theoretical Research on Structure, Reactivity of Catalytic and Physicochemical Properties as well as on Methods for Synthesis Pd-, Ni, and Cr-containing Metal Complexes, Nanoparticles, Polymers, and Materials: New Catalytic Systems, Functionalized Polymeric and Bimetallic Materials, Including Amphiphilic, Biocompatible, and Hybrid

State-funded Project by the Ministry of Science and Higher Education (Agreement № № 075-03-2020-176/3; code at the Parus 8 System FZZE-2020-0022)

The project is aimed at the development of chemical bonding formation methods with high atomic efficiency in C-C combination reactions (Mitsoroki-Heck, Suzuki-Miyaura, Sonogashira), hydrogenation, oligo-, polymerization by developing original approaches to design and investigation of fundamental bases of functioning mechanisms of palladium-, nickel- and chrome-containing metal complex and nanoscale catalysts


Due to the new standards that meet the strategy of sustainable development, the creation of new active, atom-selective and environmentally safer catalysts characterized by a reasonable ratio of selectivity and activity for various processes of unsaturated compounds transformation is a topical problem of our time. The project proposes to develop new metal-complex and nano-sized catalysts for the required processes: chemoselective hydrogenation, a number of cross-coupling reactions, polymerization of cycloolefins, aryl acetylenes, obtaining higher alpha-olefins from ethylene. In particular, chemoselective hydrogenation is one of the most important steps in the synthesis of vitamins A and E, linalool flavoring, and obtaining monomers of polymerization purity.

Currently, production of many pharmaceuticals, vitamins, flavorings and agrochemicals relies on palladium catalysts of Lindlar chemoselective hydrogenation. Low selectivity for the target product and the presence of toxic elements in its composition impose serious limitations on the use of such materials in the future. One of the modern approaches to the creation of new catalysts for chemoselective hydrogenation of acetylenic compounds is the development of low-temperature methods for the synthesis of Pd-P nanoparticles.


A. E. Favorsky Institute of Irrigation and Chemical Technology

Siberian Branch of the Russian Academy of Sciences, Moscow, Russia

A. E. Favorsky Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences

A.P. Vinogradov Institute of Geochemistry SB RAS

Quantum-chemical modeling

Study of reaction mechanisms. Computer modeling allows one to obtain a wide range of information about the molecule by submitting it to quantum chemistry calculations. Moreover, one can study mechanisms of chemical reactions, which makes it possible to explain, at the molecular level, many features and details of the reaction, for instance, characterize transition states and intermediates from the structural and energetical points of view. Knowledge of the reaction mechanism in turn allows one to control the reaction, "tune" (direct) it so as to obtain the desired product with a high yield. In some cases, it is even feasible to theoretically predict chemical compounds that are difficult or even impossible to identify experimentally, which might represent certain pharmaceutical or some other value.

Studying reaction mechanisms in the Laboratories of Quantum Chemistry and Quantum Chemical Modeling of Molecular Systems is performed in collaboration with the Laboratory of Unsaturated Heteroatomic Compounds of A.E. Favorsky Irkutsk Institute of Chemistry SB RAS, Russia.

Development and applications of the electronic structure methods. One of the key research interests of our group is the development and implementation of electronic structure methods based on Green's function (or propagator) theories, as well as the application of such methods to various problems of quantum chemistry and molecular spectroscopy. More specifically, our research pertains to the so called algebraic diagrammatic construction (ADC) approximation schemes and the methods originating from the more general intermediate state representation (ISR) concept. Green's function (propagator) formalism can be considered as an alternative to the more ordinary wave function approach.

The methods development is performed in collaboration with Prof. Dr. J. Schirmer (Theoretical Chemistry Group, Institute of Physical Chemistry, Heidelberg University, Germany) and Prof. Dr. Andreas Dreuw (Theoretical and Computational Chemistry group, the Interdisciplinary Center for Scientific Computing, Heidelberg University, Germany).

The application areas comprise valence and core ionization and excitation spectra, studies of nonadiabatic effects and highly excited states of molecular systems.