Solid State NMR studies on the mechanisms of immobilized organic-inorganic metal containing heterogeneous catalysts

• Applicant: Professor Dr. Gerd Buntkowsky
• Subject Area: Physical Chemistry of Solids and Surfaces, Material Characterisation
• Term: from 2007 to 2015
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 57198502

• Final Report Year: 2015

Final Report Abstract

Multi nuclear solid-state NMR and other physico-chemical techniques for the study of immobilized transition-metal catalysts and their interactions with substrates were developed and employed to a series of novel immobilized mono- and binuclear catalysts. The immobilized catalysts were made by covalently binding transition-metal containing catalysts to the surface of support materials such as nano-structured silica materials with different morphologies (porous or nanoparticles) or nanocrystalline cellulose via organic linkers. The catalytic activity of the catalysts was tested by model reactions, in particular hydrogenations. The main results of this project can be summarized as follows: (1) By studying a rather large range of different model systems, consisting of monomolecular and polynuclear transition metal complexes, which mimic the different scenarios of hydrogen interacting with the metal surface of a catalyst, we have established 2H-solid-state NMR spectroscopy as a diagnostic tool for the study of the interaction of hydrogen on metal surface sites and developed a correlation relation between the chemical state of the deuterium and the quadrupolar interaction. (2) The potential of homonuclear 31P-31P scalar couplings for the structural analysis of immobilized catalysts in two-dimensional solid-state NMR experiments was evaluated and successfully applied to Wilkinsons-type rhodium and ruthenium complexes. (3) Employing the sensitivity enhancement by Dynamic Nuclear Polarization (DNP), which was possible by the granting of a 400 MHz DNP solid-state NMR in a parallel project, we could establish DNP enhanced natural abundance 15N-solid-state NMR as a new tool for the characterization of immobilized catalysts without the need of expensive or chemically costly 15N isotope labeling or enrichments. (4) The following mononuclear catalysts were immobilized on silica: Wilkinson’s catalyst RhCl(PPh3)3 , RuCl2(PPh3)3 and RuHCl(CO)(PPh3)3. (5) The binuclear paddlewheel catalyst (Rh2ac4) was immobilized on porous silica and nanocrystalline cellulose support. (6) A novel self-supported dirhodium catalyst, based on the binuclear paddlewheel catalyst (Rh2ac4) was synthesized and characterized. (7) The structure of the immobilized catalysts on the support material, their binding to the support material, their interactions with substrates and the influence of macroscopic parameters such as temperature on their properties were analyzed by a combination of solidstate NMR techniques, physico-chemical characterization and quantum-chemical calculations.

Publications

• 2H Solid State NMR of ruthenium complexes. J.Am.Chem.Soc., 130,17502-17508,(2008)
  B. Walaszek, A. Adamczyk, T. Pery, Y. Xu, T. Gutmann, N. Amadeu de Sousa, S. Ulrich, H. Breitzke, H.M. Vieth, B. Chaudret, H.-H. Limbach, G. Buntkowsky
  
• “Solid State and Gas Phase NMR Studies of immobilized Catalysts and catalytic active Nanoparticles“. Topics in Catalysis, 48, 75-83, (2008)
  A. Adamczyk, Y. Xu, B. Walaszek, F. Roelofs, T. Pery, K. Pelzer, K. Philippot, B. Chaudret, H.-H. Limbach, H. Breitzke, Gerd Buntkowsky
  
• 2H-solid-state-NMR study of hydrogen adsorbed on catalytically active ruthenium coated mesoporous silica materials Solid State NMR., 35, 164-171, (2009)
  B. Walaszek, Y. Xu, A.Adamczyk, H. Breitzke, K.Pelzer H.-H. Limbach, J.Huang, H. Li, G. Buntkowsky
  
• DFT 2H quadrupolar coupling constants of ruthenium complexes: a good probe of the coordination of hydrides in conjuction with experiments Phys.Chem.Chem.Phys., 27,5657-5663 (2009)
  I.de Rosal, T. Gutmann, L. Maron, F. Jolibois, K. Philippot, B. Chaudret, B. Walaszek, H.-H. Limbach; Romuald Poteau, G. Buntkowsky
  
• Investigating Deuterium Analogues of Hydrido η 2-Dihydrogen Complexes by High Resolution 2H MAS NMR . Solid State NMR., 36 (2009) 137–143
  S. Macholl, J. Matthes, H.-H. Limbach, S. Sabo-Etienne, B. Chaudret, G. Buntkowsky
  
• 2H and 19F Solid-State NMR Studies of the Ionic Liquid C2PyBTA-d10 Confined in Mesoporous Silica Materials Phys.Chem.Chem.Phys., 12, (2010), 11371-11379
  M. Waechtler, M. Sellin, A. Stark, D. Akcakayiran, G. Findenegg, A. Gruenberg, H. Breitzke, G.Buntkowsky
  
• Hydrido-ruthenium cluster complexes as models for reactive surface hydrogen species of ruthenium nanoparticles – Solid-state 2H NMR and quantum chemical calculations. J.Am.Chem.Soc., 132, (2010), 11759-11767
  T. Gutmann, B. Walaszek, Y. Xu, M. Wächtler, I.deRosal, A.Gruenberg, R. Poteau, R. Axet, G. Lavigne, B. Chaudret, H.-H. Limbach, G. Buntkowsky
  
• Solid State NMR characterization of the Wilkinsons catalyst immobilized in mesoporous SBA-3 silica, Chemistry Eur.J., 16, (2010), 6993-6998
  A. Grünberg, Y. Xu, H. Breitzke, G. Buntkowsky
  
• 2H NMR calculations on polynuclear transition metal complexes: on the influence of local symmetry and other factors. Phys.Chem.Chem.Phys., (2011), 13, 20199-20207
  I.de Rosal, T. Gutmann, B. Walaszek, I. Gerber, B. Chaudret , H.-H. Limbach, G. Buntkowsky, Romuald Poteau
  
• Solid state NMR investigations of supported ionic liquid phase (SILP) watergas shift catalysts – ionic liquid film distribution vs. catalyst performance. Chem. Eng. Technol., (2012), 35, No. 8, 1421–1426
  M. Haumann, A. Schönweiz, H. Breitzke, G. Buntkowsky, S.Werner, N. Szesni
  
• Solid state NMR of immobilized catalysts and nanocatalysts In: Spectroscopic Properties of Inorganic and Organometallic Compounds: Techniques, Materials and Applications, (2012), 43, 289-323
  A. Grünberg, H. Breitzke, G. Buntkowsky
  
• Immobilization and Characterization of RuCl2(PPh3)3 on mesoporous Silica SBA-3. Z. Phys. Chem., (2013), 227, 901-915
  A. Grünberg, T. Gutmann, N. Rothermel, Y. Xu, H. Breitzke, G. Buntkowsky
  
• Investigation of the surface-chemistry of phosphine- stabilized ruthenium nanoparticles – An advanced solid-state NMR study. Phys. Chem. Chem. Phys., (2013), 15 (40), 17383 – 17394
  T. Gutmann, E. Bonnefille, H. Breitzke, P.-J. Debouttière, K. Philippot, G. Buntkowsky, B. Chaudret
  
• Solid-State NMR Concepts for the Investigation of supported Transition Metal Catalysts and Nano-particles. Solid State NMR, (2013), 55,1-11
  T. Gutmann, A. Grünberg, N. Rothermel, M. Werner, M. Srour, S. Abdulhussain, S. Tan, Y. Xu, H. Breitzke and G. Buntkowsky
  
• Application of Dynamic Nuclear Polarization for fast Analysis of Binding Sites of a novel Amine-Carboxyl-linked Immobilized Rhodium Catalyst. Chemistry (2015),21,3798-3805
  T. Gutmann, J.Liu, N.Rothermel, Y.Xu, E.Jaumann, H. Breitzke, S.Sigurdsson, G. Buntkowsky
  
• Design of a novel heterogeneous catalyst based on cellulose nanocrystals for cyclopropanation: Synthesis and solid-state NMR characterization. Chemistry (2015)
  J. Liu, A. Plog, P. Groszewicz, L.Zhao, Y. Xu, H. Breitzke, A.Stark, R. Hoffmann, T. Gutmann, K. Zhang, G. Buntkowsky