Synthesis And Properties Of New Ru/Os Complexes

Cancer is the second cause of death that poses a threat to human health.Chemotherapy is one of the most important means of treating cancer.Cisplatin is widely used for chemotherapy that stimulates people to study new organometallic complexes for cancer treatment.It was found that complexes based on Ru/Os have a great application potential in treating cancer.Thus,in this thesis,we synthesized new complexes of Ru/Os,and studied their structures and biological activities.Seven new dinuclear cyclic osmium-arene complexes 1-7,one new ruthenium(II)polypyridyl complex 8,five mononuclear cyclic ruthenium-arene complexes 9-13,one new dinuclear cyclic ruthenium-arene complexes 14 were prepared.The crystal structrures of complexes 1-4,9-11 and 14 were obtained.Compounds 1-14 were also characterized by 1H NMR,mass spectroscopy and elemental analysis.In the study of crystal structure of complexes 1-7,we found that the anion of the complexes plays an important role in controlling the resulting structures.When the size of the anion is small,the complexes have "boat-like" structures,when the size of the anion is large,the complexes have "chair-like" structures.CD and Agarose gel electrophoresis assay were used to study the interaction of complexes with DNA.The antitumor activity of complexes 1-5 was studied by the MTT assays.Complex 4 has good antitumor activity towards Hela.We found that complex 8 can fracture pBR322 DNA under UV irradiation and can cause the structure changes of CT-DNA.It has different fluorescence absorption under different pH.Thus,complex 8 has potentials as a fluorescence sensor for nucleic acids and an antitumor medicine.In the process of synthesizing biphenyl ruthenium complexes,we found the ligand 1,1 '-((2,4,6-trimethyl-1,3-phenylene)bis(methylene))bis(1H-pyrazole)(m-bitmb)resulted in the formation of mononuclear complex 11,the ligand 1,1'-((2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene))bis(1 H-imidazole)(p-bitmb)resulted in the formation of dinuclear complex 14.When we use[RuI2(?6-p-cymene)]2 and p-bitmb as reactants,CH2Cl2 as solvents,we still obtained complex 9.In the process of the synthesis of complex 9,we optimize the synthetic conditions.We found that the product is the same at the temperature of 140,160,180?,and the yield reaches?100%when the reaction temperature is 160 ? and the molar ratio of the metal precursor to the ligand is 1:3,and the reaction time is 72 h.When we replaced the solvent CH2Cl2 with CH2Br2 in the synthesis of complex 9,we obtained mononuclear complex 12.The toxicity of complexes 9 and 11 were studied by MTT assays.The interactions of complexes 9,11 with DNA were studied by CD and Agarose gel electrophoresis assay.We found that mononuclear ruthenium complexes have good anticancer activity,it provides a new way for synthesizing new arene-containing ruthenium complexes for antitumor researches.