TU LogoTechnische Universität Wien

Catalysis with Non-Precious Transition Metal Complexes

The development of sustainable, more efficient and selective organic synthesis is one of the fundamental research goals in chemistry. In this respect, catalysis is a key technology, since a large amount of chemical and pharmaceutical products on a laboratory and on an industrial scale are made by catalysts. However, most catalytic reactions today rely on precious metals such as ruthenium, rhodium, iridium, or palladium.

Accordingly, to develop greener, safer, and more cost-effective chemical processes it is highly important to replace precious metal catalysts by earth abundant non-precious (base) metal catalysts. Our research aims at the discovery, development, and implementation of new catalytic methodologies for opening the door to the sustainable production of pharmaceuticals and fine chemicals. Important are new catalytic approaches to efficient C-H, C-C, and C-heteroatom bond-forming reactions with well-defined non-precious metal catalysts with emphasis on V, Cr, Mn, Fe, Co, Ni, and Mo-based systems.

We intend to resolve the essential structural features of well-defined molecular homogenous catalysts in solution and mechanistic details of their function. This will include the development of new processes for the selective and sustainable transformation of abundant small molecules such as H2O, H2, N2, O2, or CO2 into high-value chemical feedstocks and energy resources. Since alcohols are accessible from indigestible biomass (lignocellulose), the development of novel catalytic reactions in which alcohols are converted into important classes of fine chemicals is a central topic of sustainable synthesis and thus plays a central role in our research. Based upon a deeper understanding and upon new insights into relationships between molecular structures and functional principles of catalysts, we hope to gain access to a rational design of new base metal catalyst.

Recent Developments

Supported Ionic Liquid Phase (SILP) Reactions - Chemoselective Hydrogenations of Aldehydes

“Chemoselective Supported Ionic Liquid Phase (SILP) Aldehyde Hydrogenation Catalyzed by an Fe(II) PNP Pincer Complex”, Brünig, J.; Csendes, Z.; Weber, S.; Gorgas, N.; Bittner, R. W.; Limbeck, A.; Bica, K.; Hoffmann, H.; Kirchner, K. ACS Catal.2018, 8, 1048-1051.

Hydrogenation of Ketones, Aldehydes, and Carbon Dioxide

“Highly Efficient and Selective Hydrogenation of Aldehydes: A Well-Defined Fe(II) Catalyst exhibits Noble Metal Activity”, Gorgas, N.; Stöger, B.; Veiros, L. F.; Kirchner, K. ACS Catal.2016, 6, 2664-2672.

Efficient and Mild Carbon Dioxide Hydrogenation to Formate Catalyzed by Fe(II)-hydridocarbonyl Complexes bearing 2,6-Diaminopyridyl Diphosphine Pincer Ligands”, Bertini, F.; Gorgas, N.; Stöger, B.; Peruzzini, M.; Veiros, L. F.; Kirchner, K.; Gonsalvi, L. ACS Catal.2016, 6, 2889-2893.

“Carbon Dioxide Hydrogenation Catalyzed by a Well-defined and Robust Hydride Mn(I) PNP Pincer Complex”, Bertini, F.; Glatz, M.; Gorgas, N.; Stöger, B.; Peruzzini, M.; Veiros, L. F.; Kirchner, K.; Gonsalvi, L. Chem. Sci.2017, 8, 5024-5029.

“Enantioselective Transfer Hydrogenation of Ketones Catalyzed by a Mn Complex Containing an Unsymmetrical Chiral PNP’ Tridentate Ligand”, Zirakzadeh, A.; de Aguiar, S. R. M. M.; Stöger, B.; Widhalm, M.; Kirchner, K. ChemCatChem2017, 9, 1744-1748.

Reactions Involving the Acceptorless Deyhdrogenation of Alcohols

Multicomponent Synthesis of Pyrimidines

“Sustainable Synthesis of Quinolines and Pyrimidines Catalyzed by Mn PNP Pincer Complexes” Mastalir, M.; Glatz, M.; Pittenauer, E.; Allmaier, G.; Kirchner, K. J. Am. Chem. Soc.2016, 138, 15543-15546.

Aminomethylation of Aromatic Compounds with Methanol as Sustainable C1 Building Block

“Mn-Catalyzed Aminomethylation of Aromatic Compounds with Methanol as Sustainable C1 Building Block”, Mastalir, M.; Pittenauer, E.; Allmaier, G.; Kirchner, K. J. Am. Chem. Soc.2017, 139, 8812-8815.

Non-classical Polyhydride Iron Complexes