Synthesis and Characterization of Self-Supported Coordination Polymer Catalysts.

• Applicant: Professor Dr. Gerd Buntkowsky
• Subject Area: Solid State and Surface Chemistry, Material Synthesis ; Physical Chemistry of Solids and Surfaces, Material Characterisation
• Term: from 2017 to 2021
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 387282605

• Final Report Year: 2021

Final Report Abstract

The main results of this project can be summarized as follows: A number of novel selfsupported coordination polymer catalysts were synthesized from chiral monomers and their structure, catalytic performance, enantioselectivity and stability were investigated. It was found that they not only achieve excellent catalytic activity in the asymmetric cyclopropanation reaction between styrene and diazooxindole but also very good enantioselectivity, stability and very good recycle properties without significant reduction in their catalytic efficiency. Employing a combination of solid-state NMR and DNP with other instrumental analytical tools, the efficacy of the synthesis and the number of defects in the resulting materials were monitored. In parallel to these main results, we also employed the solid-state NMR spectroscopy, partially combined with Dynamic Nuclear Polarization, to study in collaborative projects with other groups structural features of coordination polymers such as the incorporation of L-proline into the porous framework of the DUT-67, the connectivity between functional groups in porous polymers, the functionalization of mesoporous silica with ionic-liquid based catalysts, and catalytic surface processes in the frame work of the CO oxidation on supported Ptnanocatalysts.

Publications

• Novel Dirhodium Coordination Polymers: The Impact of Side Chains on Cyclopropanation, Catal. Sci. Technol. 8, (2018), 5190-5200
  Liu, J., Xu, Y., Groszewicz, P., Brodrecht, M., Fasel,C., Hofmann, K., Tan, X., Gutmann, T., Buntkowsky, G.
  
• Insights into the Reaction Mechanism and Particle Size Effects of CO Oxidation over Supported Pt Nanoparticles Catalysts. J. Catal. 377, (2019), 662-672
  Neumann, S., Gutmann, T., Buntkowsky, G., Paul, S., Thiele, G., Sievers, H., Bäumer, M., Kunz, S.
  
• Insights into the Role of Zirconium in Proline Functionalized Metal-Organic Frameworks attaining high Enantio- and Diastereoselectivity. J. Catal. 377, (2019), 41-50
  Nguyen, K., Kutzscher, C., Ehrling, S., Senkovska, I., Bon. V., de Oliveira Jr., M., Gutmann, T., Buntkowsky, G., Kaskel, S.
  
• Room temperature CO oxidation catalysed by supported Pt nanoparticles revealed by solidstate NMR and DNP spectroscopy. Catal. Sci. Technol. 9, (2019), 3743–3752
  Klimavicius, V., Neumann, S., Kunz, S., Gutmann, T., Buntkowsky, G.
  
• A comprehensive approach for the Characterization of Porous Polymers by 13C and 15N Dynamic Nuclear Polarization NMR Spectroscopy. Phys. Chem. Chem. Phys. 22, (2020), 23307-23314
  Grätz, S., de Oliveira Jr., M., Gutmann, T., Borchardt, L.
  
• Coordination compounds of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) ligands: Extremely high thermostability and ligand oxidation in solid state Eur. J. Inorg. Chem. (2020), 2444-2456
  D. Goedderz, T.Schäfer, J. Klitsch, L. Weber, B.Weber, O. Fuhr, G. Buntkowsky, F. Schönberger, M. Döring
  
• Dirhodium Coordination Polymers for Asymmetric Cyclopropanation of Diazooxindoles with Olefins: Synthesis and Spectroscopic Analysis. ChemPlusChem 85, (2020), 1737-1746
  Li, Z., Rösler, L., Herr, K., Brodrecht, M., Breitzke, H., Hofmann, K., Limbach, H.-H., Gutmann, T., Buntkowsky, G
  
• SBA-15 supported imidazolium ionic liquid through different linkers as sustainable catalyst for synthesis of cyclic carbonates: A kinetic study and Theoretical DFT calculations Ind. Eng. Chem. Res. 59, (2020) 12632-12644
  M. Ghiaci, Z.Dokhaie, H. Farrokhpour, G. Buntkowsky, H. Breitzke
  
• Design and Characterization of Novel Dirhodium Coordination Polymers - The Impact of Ligand Size on Selectivity in Asymmetric Cyclopropanation. Catal. Sci. Technol. 11, (2021), 3481-3492
  Li, Z., Rösler, L., Wissel, T., Breitzke, H., Hofmann, K., Limbach, H.-H., Gutmann, T. Gerd Buntkowsky
  
• Immobilization of a Chiral Dirhodium Catalyst on SBA-15 via click-chemistry: Application to Asymmetric Cyclopropanation of Diazooxindoles. J. CO2 Utilization (2021)
  Li, Z., Rösler, L., Wissel, T., Breitzke, H., Gutmann, T., Buntkowsky, G.