Projects / Programmes source: ARIS

Metal Complexes of Tetradentate Pyridyl-Mesoionic Carbenes as Potential Catalysts for Polymerization

Research activity

Code Science Field Subfield
1.04.04  Natural sciences and mathematics  Chemistry  Organic chemistry 

Code Science Field
P395  Natural sciences and mathematics  Organometallic chemistry 

Code Science Field
1.04  Natural Sciences  Chemical sciences 
Mezoionski karbeni, triazolilideni, ciklični, aciklični, tetradentatni, kompleksi, železo, kataliza, polimerizacija, mehanistične študije
Evaluation (rules)
source: COBISS
Researchers (1)
no. Code Name and surname Research area Role Period No. of publicationsNo. of publications
1.  34350  PhD Aljoša Bolje  Chemistry  Head  2017 - 2019  45 
Organisations (1)
no. Code Research organisation City Registration number No. of publicationsNo. of publications
1.  0104  National Institute of Chemistry  Ljubljana  5051592000  21,277 
This project is based on recent discoveries that Mesoionic Carbenes (MICs), especially the ones based on triazolylidenes (trzNHC; triazolium N-heterocyclic carbene) possess a unique complexation ability to transition metals. Complexes of trzNHCs are increasingly used in homogenous metal-based catalysis, as well as for photophysical and biochemical purposes. Nontheless, there is a lack of bi- and poly-dentate ligands of such type, especially in term of cyclic ones. We plan to prepare novel cyclic and acyclic tetradentate MIC ligands having two triazolylidene and two pyridine or all triazolylidene donors and to determine their coordination abilities. Moreover, iron complexes, for whose stability multidentate ligands are essential, bearing these MIC-ligands will be prepared in order to study their electronic properties and catalytic abilities. The studies aim also at understanding the cataytic and electronic properties by examing the compounds with modern spectro-electro chemical and magnetic methods, as well as to gain insights into the catalytic mechanisms. Polymerization will be the main reaction within the catalytic part of the projected studies. We will target the Metal-catalyzed living radical polymerization (Mt-LRP) with iron(II) as a metal source. We also plan to compare the catalytic activity of iron(II) complexes with their ruthenium(II) analogues, which will be also synthesized, and hopefully be able to use the cheap and abundant iron for executing the above catalysis. Iron has also relatively low toxicity and hence it is benign to the environment. Once we will obtain successful results with simple substrates (monomers), we will then also test the most active catalysts for functional substrates and substrates that are relevant for the chemical and pharmaceutical industries. The project utilizes a modern approach in the rational design of novel catalysts as it incorporates principles of known type of organic synthesis to generate challenging and novel ligand classes and extends them into the field of inorganic chemistry, electronic structures and catalysis. The project will be extensively supported by collaborating researchers within the Department of Polymer Chemistry and Technology, at the National Institute of Chemistry and by interaction of the fellow with worldwide collaborators from cooperation projects in the fields of inorganic, organic, physical and polymer chemistry, as well as physics. The combined expertise of the Department and the researcher will allow the successful realization of this modern and contemporary project. It is expected to contribute significantly to the progress in organometallic chemistry, physical inorganic chemistry and catalysis (mostly polymerization catalysis) with posible impacts for the chemical and pharmaceutical industries, molecular materials and to the qualification of the researcher.
Significance for science
Although, the catalysis with transition metal complexes is of a high interest among science and industry the research and development of this field of chemistry is still emerging. Moreover, the development of new catalytic system, as well as understanding the mechanisms of such reactions for developing suitable catalysts and systems for certain reaction is very important. The proposed project is expected to contribute significantly to the progress in the field mentioned above by developing new organic ligands, derived from the N-heterocyclic carbenes (NHCs) that are suitable for coordination to transition metals. More in detail, the proposed research is expected to have impact in the field of organometallic, physical inorganic chemistry and catalysis, especially in polymerization catalysis. If successful, the project should also show the enormous potential of organic ligands and organometallic compounds within the fields of catalysis and synthetic chemistry, with possible impacts for the chemical and pharmaceutical industries, as well as material science. The training goals are well within the current trends in chemistry of NHC ligands. However, the project ventures into relatively unexplored fields of tetradentate cyclic and acyclic ligands, having triazolium NHC (trzNHC) C-donors and heterocyclic N-donors, as well as into the less explored world of polymerization catalysis with iron, a more sustainable and attractive metal, which could be also the metal of the future. The reasearch field is of an interdisciplinary nature. Hence, the obtained results are expected to be published in high quality peer-reviewed journals. Open access journals will be also taken in consideration. Relatively high journal impact factor is expected, due to the topic, based on catalysis. The long term goal is to establish these ligand classes and metal complexes in different branches of catalysis and switchable materials.
Significance for the country
Despite the majority reactions and processes in the industry still run with renowned catalysts, a need for the new representatives and catalytic systems is undisputed. Far too few new examples have been developed and are in use in nowadays industrial processes. Therefore, we need to develop new compounds with improved catalytic efficiency and broader spectrum of application. Hence, also the design of new complexation agents is very important. The industrial research will not be able to manage and develop all this. In alternative, it would be beneficial to establish this field of research extensively at the academic institutions. The short term goal of the projected studies is the successful fulfillment of this project with possible impacts for the chemical and pharmaceutical, as well as material industries. The metal-catalyzed living radical polymerization (Mt-LRP) has become very popular in synthesis of controlled polymers with well-defined primary structures, but also for advanced architectures construction. Being a resourceful metal, which is usually relatively easy to remove from products and also recyclabe, as well as abundant and less harmful to human, iron jump in front of many others on the list of wanted metals for catalysis within the industrial world, despite being to date not so active in comparison to some other ions. Thus, a highly active iron-based Mt-LRP system would be very attractive for application in industrial way, for example in producing materials or for pharmaceutical purposes. It will lower the price plus will be more safe and bio-compatible. Discover and further development of such catalysts can have a great direct impact on economy, as well as society. Hence, the protection by patents will be also taken in consideration where possible, due to the over-all interest to industry. There are still places for improving the polymerization catalysis but on the other side a catalytic system, based on a sustainable metal which iron defenitely is, would promote metal-catalyzed living radical polymerization also for practical applications in industry.
Most important scientific results Final report
Most important socioeconomically and culturally relevant results Final report
Views history