Synthesis, Crystal Structures And Bioactivities Of Ferrocene Pyrazole Carboxylic Acid Metal Complexes

The ferrocene and ferrocenyl derivatives have attracted special attention because of their unique structure and natures. They have broad application prospects. especially in biology, medicine and other fields, Many ferrocenyl compounds display interesting anti-tumor, antifungal, antimalarial, pesticide, antianemic and enzyme inhibitor activity. In this dissertation, the studies on the bioactivity of the ferrocene and its derivatives have been reviewed in detail, and a ligand containing N, O atoms named 3-trifluoromethyl-5-ferrocenyl-pyrazol-1-yl-acetic acid (LCOOH) has been designed, synthesized and characterized, and a series of new complexes of the ligand were synthesized. These complexes were characterized by IR, elemental analysis,1H NMR, UV-Vis and crystal X-ray diffraction methods. We mainly studied the crystal structures, electrochemical properties and the bioactivities. The main work is listed as following:1. Synthesis, crystal structures and bioactivities of organotin oxo clusters containing ferrocenyl and pyrazolyl moiety.Three organotin oxo clusters containing ferrocenyl and pyrazolyl moiety [Ph4Sn2O(OCH3)(OOCL)]2, [BuSnO(OOCL)]6 and [Bu4Sn2O(OOCL)2]2 were synthesized by the reaction the ligand (LCOOH) with Ph3Sn(OH), n-BuSnOOH and n-Bu2SnO respectively. Crystal structures of complexes [Ph4Sn2O(OCH3)(OOCL)]2 and [Bu4Sn2O(OOCL)2]2 are centro-symmetric ladder framework and Complex [BuSnO(OOCL)]6 displays a hexanuclear one with drum structure. Only one broad voltammetric wave appeared in the each complex cyclic voltammetry measurements. This indicates that the ferrocene moieties in the complexes are almost identical and there is little interaction between them. Antitumor activities of these compounds were also evaluated, by using HepG2 human hepatocellular liver carcinoma cells, A549 human lung carcinoma cells and B16-F10 melanoma cells. The results indicate the three organotin complexes have a good activity against all the three tumor cell lines, and even stronger than the corresponding precursor. The complex [Ph4Sn2O(OCH3)(OOCL)]2 the best cytotoxicity, even more active than "cisplatin". It may be a promising substrate to be subject of further investigations. Thus, it is conceivable that the tin atom and the ligand could act synergistically.2. Synthesis, crystal structures and bioactivities of copper(Ⅰ), silver(Ⅰ) and gold (Ⅰ) complexes containing ferrocenyl and pyrazolyl moiety.The sencond ligand Bis(diphenylphosphino)methane (dppm) was introduced and the precursors [Cu2(dppm)2](NO3)2, [Ag2(dppm)2](NO3)2 and [Au2(dppm)2](Cl)2] were synthesized. Then, [Cu3(dppm)3O(OOCL)], [Ag2(dppm)2(OOCL)2] and [Au2(dppm)2(OOCL)2], which Copper(Ⅰ), silver(Ⅰ), gold (Ⅰ) complexes containing ferrocenyl and pyrazolyl moiety were synthesized by the reaction of them with ligand (LCOOH). Crystal structures shows that [Cu3(dppm)3O(OOCL)] is trinuclear oxygen atom-capped cluster, and the ligand carboxyl group bridging two copper atoms. [Ag2(dppm)2(OOCL)2] and [Au2(dppm)2(OOCL)2] are binuclear complexes. The former ligand are monodentate, the latter LCOO- and [Au2(dppm)2]2+ is mainly connected by the weak interaction. Compared with cyclic voltammetry curves of the ligand, those of the complexes exhibit similar redox processes, This is attributed to the ferrocene group. The half-wave potential value of [Cu3(dppm)3O(OOCL)] and [Ag2(dppm)2(OOCL)2] are more negative, but [Au2(dppm)2(OOCL)2] is little changed, indicating that [Au2(dppm)2(OOCL)2] may dissociate in the solution. Antitumor activities of some compounds were also evaluated by using HepG2, A549 and B16-F10. The result show that the complexes [Cu3(dppm)3O(OOCL)] and [Ag2(dppm)2(OOCL)2] have a good activity and stronger than the corresponding precursor and ligand. The complex [Cu3(dppm)3O(OOCL)] displayed the best cytotoxicity, even more active than "cisplatin". It may be a promising substrate to be subject of further investigations. Thus, it is conceivable that the metal atom and the ligand could act synergistically.