Development of Integrated Multinuclear Transition Metal Complexes with Novel Properties

(1)新型可逆添加分子氧的双核铁(II)、钴(II)配合物的研制：我们成功地合成了第一个可逆添加分子氧的双核铁配合物[Fe_2(Ph-bimp)(C_6H_5COO)(O_2)]^&lt；这个建筑群引起了全世界的关注。二钼超氧双核钴配合物[(Me_3Tacn)_2CO^&lt；III&gt；2(Mu-OH)(Mu-O_2)]^&lt；3+&gt；(2)具有吸氧能力的铜(I)络合物的制备及其催化氧化性能：[Cu(N_4-Me_3PY)]^+与分子氧反应，配体的a-CH_3-被氧化成-COOH。[Cr(H^2O)(TPA)]^+是将NO_2还原为N_2O的良好催化剂。(3)双核铬(III，III)-，双核铬(III)-镍(II)-，三核镍(II，II)-铬(O)络合物；合成了金属-金属超交换作用及分子磁体的发展：[(Phen)_2Cr-(OH)_2Ni(L_2)]^&lt；3+&gt；(L_2：2，2，2-tet，3，2，3-tet，Cyclen，TPA，Me-TPA，Me_2-TPA)，并研究了镍(II)和铬(III)离子之间的磁性相互作用。在现阶段，我们还无法制备出理想的分子磁体。新合成了[Ni_2(Me_4-tpdp)(CH_3COO)(ClO_4)(CH_3OH)]^+和[Ni_2(Me_4-tpdp)(CH_3COO)(尿素)]^&lt；2+&gt；(5)双核锌(II，II)配合物作为磷酸酯酶模型的研究进展：[Zn_2(Me_4-tpdp)(HOCOO)]^&lt；2+&gt；，[Zn_2(Me_4-tpdp)(CH_3OCOO)]^&lt；2+&gt；，[Zn_2(Me_4-tpdp)(OH_2)]^&lt；，和[Zn_2(Me_4-tpdp)(OH_2)]^&lt；2+&gt；是一个很好的磷酸酶模型。

(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.