Artifizielle Metalloenzyme und heterogenisierte Übergangsmetall-Komplexe mit Triphos-Liganden : Synthese, Kupplungsstrategien und katalytische Aktivität

  • Artificial metalloenzymes and heterogenized transition metal complexes with Triphos ligands: Synthesis, coupling strategies and catalytic activity

Krystof, Monika; Leitner, Walter (Thesis advisor); Klankermayer, Jürgen (Thesis advisor)

Aachen (2016)
Dissertation / PhD Thesis

Dissertation, RWTH Aachen University, 2016


This doctoral thesis deals with artificial metalloenzymes and heterogenized transition metal complexes with Triphos ligands.In the first part of this work the Triphos ligand was modified and different functional groups were introduced in the ligand backbone for later covalent anchoring. By this the Triphos alcohol ligand and the Triphos aldehyde ligand were accessible.In the second part of this thesis coupling strategies were developed on the basis of these two ligands. For the heterogenisation of transition metal complexes the Triphos alcohol ligand was covalently tethered onto benzoic acid functionalized polystyrene by Steglich esterification. Subsequent complexation reactions with ruthenium and rhodium precursors lead to heterogenized complexes. These complexes were tested successfully in different hydrogenation reactions. In addition, PHIP experiments were conducted with success with the heterogenized rhodium complexes.For the synthesis of artificial metalloenzymes the Triphos aldehyde ligand took center of stage in the investigations. First it was complexated with rhodium precursors and then it was covalently tethered by a hydrazone bond to the protein FhuA which was provided with a maleimid hydrazide linker in the first place. The obtained artificial metalloenzyme was tested in hydrogenation reaction as well in methanol as in water. In both reaction media it showed high activity and long stability. In addition, the first known PHIP experiments were conducted with an aritifical Metalloenzyme in methanol and water and were positive.


  • Chair of Technical Chemistry and Petrochemistry [154110]
  • Department of Chemistry [150000]