Leila Taghizadeh Ghoochany

• The scientific intention of this work was to synthesize and characterize new bidentate, tridentate and multidentate ligands and to apply them in heterogenous catalysis. For each type of the ligands, new methods of synthesis were developed. Starting from 1,1'-(pyridine-2,6-diyl)diethanone and dimethylpyridine-2,6-dicarboxylate different bispyrazolpyridines were synthesized and novel ruthenium complexes of the type (L)(NNN)RuCl2 could be obtained. The complexes with L = triphenylphosphine turned out to be highly efficient catalyst precursors for the transfer hydrogenation of aromatic ketones. Introduction of a butyl group in the 5-positions of the pyrazoles leads to a pronounced increase of catalytic activity. To find a method for the synthesis of bispyrimidinepyridines, different reactants and condition were applied and it was found that these tridentate ligands can be obtained by mixing and grinding the tetraketone with guanidinium carbonate and silica, which plays the role of a catalyst in this ring closing reaction. The bidentate 2-amino-4-(2-pyridinyl)pyrimidines were synthesized from different substrates according to the desired substituent on the pyrimidine ring. Reacting these bidentate ligands with the ruthenium(II) precursor [(η6-cymene)Ru(Cl)(μ 2-Cl)]2 gave cationic ruthenium(II) complexes of the type [(η6-cymene)Ru(Cl)(adpm)]Cl (adpm = chelating 2-amino-4-(2-yridinyl)pyrimidine ligand). Stirring the freshly prepared complexes with either NaBPh4, NaBF4 or KPF6, the chloride anion was exchanged against other coordinating anions (BF4-, PF6-, BPh4-).Some of these ruthenium complexes have shown very special activities in the transfer hydrogenation of ketones by reacting them in the absence of the base. This led to detailed investigations on the mechanism of this reaction. According to the activities and with the help of ESI-MS experiments and DFT calculations, a mechanism was proposed for the transfer hydrogenation of acetophenone in the absence of the base. It shows that in the absence of the base, a C-H bond activation at the pyrimidine ring should occur to activate the catalyst. The palladium complexes of bidentate N,N ligands were examined in coupling reactions. As expected, they did not show very special activities. Multidentate ligands, having pyrimidine groups as relatively soft donors for late transition metals and simultaneously possessing a binding position for a hard Lewis-acid, could be obtained using the new synthesized bidentate and tridentate ligands.