Control of Reactivies of Mononuclear Iron Complexes by Design of Their Ligands

按照计划实施了三个项目。配体结构及其配位方式对配体脱氢反应的控制：制备了三氮（三胺）高铁酸盐（II）和（III）配体并对其结构进行了表征。特别是二（吡啶基甲基）胺与铁的配位模式，聚合物和面配位模式对反应活性有很大影响，前者脱氢顺利，后者则有阻力。博来霉素模型配合物的结构和反应性：为了提高抗癌药物博来霉素金属结合位点抗氧化破坏的稳定性，合成了多甲基化的博来霉素模型配体。制备了具有新配体的Fe（II）、Fe（III）、Cu（II）、Zn（II）配合物。随着甲基取代次数的增加，Cu（II）和Zn（II）的整体结构有由方金字塔向三角双金字塔转变的趋势。但甲基化对dna的氧化裂解能力较弱。铁（II）与1,3-二亚胺基中心碳与铁的四齿配体之间的腈桥接反应：以2,4-戊二酮和2-氨基甲基吡啶为原料，通过铁介导的模板反应制备了一种符合要求的配体。该配合物的腈溶液通过在腈和四齿配体的碳原子之间形成C-C键生成了一系列新的含五齿配体的铁配合物。该反应也适用于多种腈。与五齿酸配体的铁配合物在过氧化氢的作用下产生过氧化氢，并能氧化切割DNA。

Three projects were carried out according to the plan.1.Control of Dehydrogenation Reactions of Ligands by the structure of Ligands and their Coordination Mode : The tricyano (triamine) ferrates (II) and (III) with them were prepared and their structures were charcterized. Especially, the coordination mode of di (pyridylmethyl) amine to iron, mer-and fac-coordination mode, strongly influenced on the reactivity : the former underwent smooth dehydrogenation but the latter resisted.2.The Strucure and Reactivity of Bleomycin Model Complexes : Polymethylated bleomycin model ligands were synthesized to improve the stability of the metal binding site of the anti cancer drug of bleomycin against oxidation destruction.Fe(II), Fe(III), Cu(II), Zn(II) complexes with new ligands were prepared. As the number of methyl substitution is increased, the overall structures of Cu(II) and Zn(II) tend to change from square-pyramid to trigonal bipyramid. But the methylation rendered less capability in oxidative cleavage of DNA.3.Bridging Reaction of Nitrles between Iron(II) and the Central Carbon of 1,3-Diimine Group Incorporatrd to the Tetradentate Ligands of the iron : One ligand was designed to fullfill the requirement and was prepared by an iron-mediated template reaction from 2,4-pentanedione and 2-aminomethylpyridine. Nitrile solution of this complex yielded new series of iron complexes with pentadentate ligands fomed via C-C bond formation between nitriles and the carbon atoms of the tetradentate ligands. This reaction is also applicable to a wide range of nitriles. The iron complexes with pentadentate ligands yielded hydroperoxide species on addition of hydrogen peroxide and are capable to cleave DNA oxidatively.