Übergangsmetallkomplexe mit basischen N-Donor-Liganden in Katalyse und medizinischer Chemie

This work describes the synthesis, characterization and application of transition metal complexes with highly basic N-donor ligands in catalysis and medicinal chemistry. The main focus are the complexes of the proton sponges quino[7,8-h]quinolines. These compounds show many exciting properties: high thermal stability (>320 °C), high chemical stability (conc. sulphuric acid) and an extreme “out-of-plane” position of the complexed transition metal atom. The palladium complexes of the quino[7,8-h]quinolines as well as complexes of various naphthyridines have been studied as Heck, Suzuki and amination catalysts. The catalysts were well dispersed in / on the mesoporous silicon dioxide SBA-15, too. A combinatorial testing of the reaction conditions included microwave radiation as a heat source. The palladium complexes of 4,9-dichloroquino[7,8-h]quinoline are excellent Heck catalysts and effective catalysts for Suzuki and amination reactions. Interestingly, this lead to a study of the Heck reaction mechanism by DFT-methods. The calculations showed that the Pd(0)-complexes of quino[7,8-h]quinoline have an unusual binding pattern because the palladium atom is not symmetrically arranged between the two nitrogen atoms. The heterogenization of this complex in SBA-15 leads to an increase of the turnover number by around 200 %. The interactions of the platinum and rhenium complexes of quino[7,8-h]quinolines with DNA have been studied. The platinum complex intercalates specifically in mismatch DNA and binds there, while the rhenium complex shows a light switch effect with calf thymus DNA. Furthermore, the cytostatic activities of the platinum complexes with quino[7,8-h]quinolines have been studied. High activities could be found for lung cancer and uterus cancer cells.