Development of Integrated Multinuclear Transition Metal Complexes with Novel Properties

具有新性能的集成多核过渡金属配合物的开发

• 批准号: 08640707
• 负责人: UEHARA Akira
• 金额: $ 1.41万
• 依托单位: Faculty of Science, Kanazawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08640707/
• 关键词: Dinuclear Cobalt Complexes; Dinuclear Iron Complexes; Dinuclear Nickel Complexes; Tetranuclear Iron Complexes; Molecular Oxygen Complexes; Dinuclear Zink Complexes; Magnetic Interaction; 分子状酸素; 二核化配位子; 酸素錯体; クロム(III)-ニッケル(II)錯体; 磁気交換相互作用

(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.

(1)以铁蛋白为模型的新型双核铁（II）和钴（II）配合物的研制：成功制备了首个可可逆添加分子氧的双核铁配合物[Fe_2 (Ph-bimp) (C_6H_5COO) (O_2)]^<2+>。这个建筑群引起了全世界的注意。新制备了二-mu-超氧双核钴配合物[(Me_3 - tacn)_2 CO^<III>_2(mu-OH) (mu-O_2)]^<3+>，其特点是含有两个桥接的超氧基团。(2)吸附氧配合物铜(I)的制备及其催化氧化能力：[Cu (N_4-Me_3py)]^+与分子氧反应，配体的a - CH_3 -被氧化为- 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) -和三核镍（II，II） -铬(O)配合物的制备合成了[(phen)_2Cr- (OH)_2Ni (L_2)]^<3+> （L_2: 2,2,2-tet, 3,2,3-tet, cyclen, tpa， Me-tpa和Me_2-tpa）分子磁体，并研究了镍（II）与铬（III）离子之间的磁相互作用。在现阶段，我们还不能制备出理想的分子磁铁。然而，这一结果将为分子磁体的发展提供一个良好的方向。(4)作为脲酶模型的镍（II）配合物的制备：新制备了[Ni_2 (Me_4-tpdp) (CH_3COO) (ClO_4) (CH_3OH)]^+和[Ni_2 (Me_4-tpdp) (CH_3COO)（尿素）]^<2+>，并对其结构进行了分析。该配合物将成为脲酶的良好模型。(5)双核Zink （II，II）配合物作为磷酸酶模型的发展：新制备了[Zn_2 (Me_4-tpdp) (HOCOO)]^<2+>, [Zn_2 (Me_4-tpdp) (CH_3OCOO)]^<2+>, [Zn_2 (Me_4-tpdp) (OH_2)]^<3+>和[Zn_2 (Me_4-tpdp) (OH_2)]^<2+>，这将是一个很好的磷酸酶模型。

项目成果

H.Sugimoto, Y.Hayashi, C.Koshi, S.Fujinami, M.Suzuki, Y.Maeda, and A.Uehara: "Formation of a Tetranuclear High-Spin Iron (II,III,II,III) Mixed Valence Complex" Chem.Lett.No.10. 933-934 (1996)

H.Sugimoto、Y.Hayashi、C.Koshi、S.Fujinami、M.Suzuki、Y.Maeda 和 A.Uehara：“四核高自旋铁 (II,III,II,III) 混合价络合物的形成

N.Komeda,H.Nagao,Y.Kushi,G.Adachi,M.Suzuki,A.Uehara,& K.Tanaka: "Molecular Structure of Nitro-and Nitrito-Copper Complexes as Reaction Intermediates in Electro-chemical Reduction of Nitrite to Dinitrogen oxide" Bull.Chem.Soc.Jpn.68・2. 581-589 (1995)

N.Komeda、H.Nagao、Y.Kushi、G.Adachi、M.Suzuki、A.Uehara 和 K.Tanaka：“硝基和亚硝基铜配合物作为亚硝酸盐电化学还原反应中间体的分子结构氧化二氮” Bull.Chem.Soc.Jpn.68・2.581-589 (1995)

T.Ookubo, H.Sugimoto, T.Nagayama, H.Masuda, T.Sato, K.Tanaka, Y.Maeda, H.Ohokawa, Y.Hayashi, A.Uehara, & M.Suzuki: "Cis-1,2-μ-Peroxo Diiron Complex: Structure and Reversible Oxygenation" J.Am.Chem.Soc.118・3. 701-702 (1996)

T.Ookubo、H.Sugimoto、T.Nagayama、H.Masuda、T.Sato、K.Tanaka、Y.Maeda、H.Ohokawa、Y.Hayashi、A.Uehara 和 M.Suzuki：“Cis-1， 2-μ-过氧二铁配合物：结构和可逆氧化” J.Am.Chem.Soc.118・3.701-702 (1996)

H.Sugimoto, Y.Hayashi, C.Koshi, S.Fujinami, M.Suzuki, Y.Maeda, & A.Uehara: "Formation of a Tetranuclear High-Spin Iron(II,III,II,III) Mixed Valence Complex" Chem.Lett.1996・10. 933-934 (1996)

H.Sugimoto、Y.Hayashi、C.Koshi、S.Fujinami、M.Suzuki、Y.Maeda 和 A.Uehara：“四核高自旋铁 (II,III,II,III) 混合价配合物的形成《化学快报》1996・10.933-934 (1996)

Y.Hayashi, M.Obata, M.Suzuki, and A.Uehara: "Synthesis and Properties of Di-mu-superoxo Dinuclear Cobalt (II,III) Complex" Chem.Lett.No.12. 1255-1256 (1997)

Y.Hayashi、M.Obata、M.Suzuki 和 A.Uehara：“Di-mu-超氧双核钴 (II,III) 配合物的合成和性质”Chem.Lett.No.12。