Sustainable routes to amines and nitrogen-containing organic molecules using non-precious metal catalysts

​Grant funding 2022-2024
Ministry of Education and Sciences

The aim of the project is to develop novel efficient metal-ligand cooperative catalysts with readily available and non-toxic metal precursors and polydentate amine ligands for interconversion of nitrogen-containing organic functionalities and preparation of amines from readily available feedstock.

The project fits well with the global research in economical and environmentally benign catalytic technologies for production of commodity and fine chemicals. Such technologies have very high economic and social impact, minimizing production costs for chemical products, as well as minimizing waste production. The project is a fundamental research in natural sciences (chemistry, catalysis, inorganic chemistry, organic chemistry; physical chemistry, computational chemistry) and aims at the study of novel economical catalytic systems for synthesis of amines, widely used as building blocks in the synthesis of biologically active molecules, natural products, pharmaceuticals, agrochemicals, etc. Considering the importance of amines in modern organic synthesis, these new sustainable technologies serve as attractive alternatives to conventional wasteful techniques for production of amines based on stoichiometric transformations.

The catalyst design will be based on the combination of both metal-ligand cooperativity and hemilability concepts will allow to develop catalytic systems with enhanced activity and selectivity, while maintaining the necessary catalyst stability. Studies of stoichiometric and catalytic reactivity of the proposed systems as well as understanding the mechanisms of these reactions will allow to evaluate these catalysts for industrial applications and envision preparation of more active systems with predictable properties and reactivity. The obtained catalysts will be tested in catalytic hydrogenation reactions for preparation of amines and their derivatives. In addition, the proposed catalytic systems will be applied to many other synthetically important reactions, relevant to production of value-added nitrogen-containing products, such as functionalization of amines via hydroamination reactions (one of the most attractive and the most atom-economical transformation for preparation of amine derivatives) as well as selective production of amides by catalytic hydration of readily available nitriles. The latter products occur in a large variety of biologically active compounds, pharmaceuticals, pesticides, herbicides, polymers and synthetic intermediates, and the development of atom-efficient and selective production of amides spawn considerable interest of synthetic chemistry community and industry. Overall, the results of the project will be of interest to specialty chemical industry, which focuses on production of high value organic products. Moreover, the obtained results will be also of relevance to technologies for hydrogen storage and transportation, which are tightly connected to hydrogen economy and the concept of decarbonization of fossil fuels. For instance, such molecules as formaldehyde, formic acid, ammonia-borane and even water, which will be utilized as hydrogen sources in reduction catalysis within this project, are considered as viable hydrogen storage materials and their efficient onsite dehydrogenation is an important task to address in the light of hydrogen transfer and storage.
So far, a series of organometalic manganese, iron and nickel catalysts/precataysts based have been prepared, and their catalytic activity in target reactions is currently under investigation.