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

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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.