Development of Integrated Multinuclear Transition Metal Complexes with Novel Properties

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(1) Development of Novel Dinuclear Iron (II) and Cobalt (II) Complexes Which Can Reversibly Add Molecular Oxygen as a Model of Iron Protein : We succeeded in preparing the first dinuclear iron complex [Fe_2 (Ph-bimp) (C_6H_5COO) (O_2)]^<2+> which can reversibly add molecular oxygen. The complex was noticed worldwide. Di-mu-superoxo dinuclear cobalt complex [(Me_3 tacn)_2 CO^<III>_2(mu-OH) (mu-O_2)]^<3+> was newly prepared, which is characteristic in that it contains two bridging superoxo groups.(2) Preparation of Copper (I) Complexes Which Can Absorb Oxygen and Catalytically Oxidizing Abilities Thereof : [Cu (N_4-Me_3py)]^+ was reacted with molecular oxygen, and the a CH_3 - group of the ligand was oxidized to -COOH.[Cr(H^2O) (tpa)]^+ was found to be a good catalyst for reducing NO_2 to N_2O.(3) Preparation of Dinuclear Chromium (III,III) -, Dinuclear Chromium (III) -Nickel (II) -, and Trinuclear Nickel (II,II) -Chromium (O) Complexes ; Metal-Metal Superexchange Interaction, and Development of Molecular Magnets : [(phen)_2Cr- (OH)_2Ni (L_2)]^<3+> (L_2 : 2,2,2-tet, 3,2,3-tet, cyclen, tpa, Me-tpa, and Me_2-tpa) were synthesized, and investigated the magnetic interaction between nickel (II) and chromium (III) ions. In the present stage, we could not prepare an ideal molecular magnet. However, the results here will be a good direction for devel-oping a molecular magnet.(4) Preparation of Nickel (II) Complexes as Model of Urease : [Ni_2 (Me_4-tpdp) (CH_3COO) (ClO_4) (CH_3OH)]^+ and [Ni_2 (Me_4-tpdp) (CH_3COO) (urea)]^<2+> were newly prepared and the structure was analyzed. The complexes will be a good model of urease.(5) Development of Dinuclear Zink (II,II) complexes as a Model of Phosphoesterase : [Zn_2 (Me_4-tpdp) (HOCOO)]^<2+>, [Zn_2 (Me_4-tpdp) (CH_3OCOO)]^<2+>, [Zn_2 (Me_4-tpdp) (OH_2)]^<3+>, and [Zn_2 (Me_4-tpdp) (OH_2)]^<2+> were newly prepared, which will be a good model of phosphatase.