Syntheses and Reactivity of Diiorn-, Dicobalt-, and Dicopper-Dioxygen Complexes

Diiorn-、二钴-和二铜-双氧配合物的合成和反应性

• 批准号: 07454175
• 负责人: SUZUKI Masatatsu
• 金额: $ 4.86万
• 依托单位: KANAZAWA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454175/
• 关键词: Diiron-Dioxygen Complexes; Dicopper-Dioxygen Complexes; Dioxygen Affinity; Crystal Structures; Reversible Oxygenation; Equilibrium; Thermodynamic Parameters; 二核鉄錯体; 二核鉄酸素錯体の結晶構造; 生物無機化学; 非ヘム鉄; 酸素化; 酸化反応; 熱的安定性; 非ヘムタンパクモデル錯体; ヘムエリスリンモデル錯体

Diiron-dioxygen and dicopper-dioxygen complexes play an important role in the reversible binding and activation of O_2 in biological and catalytic processes. We developed various diiron (II) and dicopper (I) complexes as functional models for O_2 transport proteins such as Hemerythrin (Fe_2) and hemocyanin (Cu_2) and mono-oxygenase such as methane monooxygenases (Fe_2 or Cu_n).Diiron Complexes : Only a few structurally and spectroscopically characterized diiron-dioxygen complexes have been reported. In order to synthesize the diiron-dioxygen complexes, it is important to control the ligand environment which is suitable for O_2 binding by two iron ions and stabilizes the mu-peroxo species toward irreversible oxidation. For this purpose, a series of dinucleating ligands with sterically hindered pyridyl and imidazolyl groups has been developed, which has an N_6O donor set with a phenolate or alkoxide bridging group. They form five-coordinate dinuclear [Fe_2 (L) (RCO_2)]^<2+> with an exoge … More nous carboxylate bridge, which react with O_2 to form mu-peroxo species. It was found that thermal stability toward irreversible oxidation and dioxygen affinity of those complexes are highly dependent on the stereochemistry and the electron donor ability of dinucleating ligands and bridging carboxylate. Finally we have succeeded in preparation and structural characterization of a cis-mu-1,2-peroxo diiron complex which is the first example of a crystallographically characterized diiron-dioxygen complex that binds O_2 reversibly at ambient temperature.Dicopper Complexes : A series of copper (I) complexes ([Cu (L)]^+) having tripodal tetradentate ligands ((R_1R_2NCH_2CH_2)_3N : L) was synthesized. Reactivity of those complexes with O_2 was investigated. They form trans-mu-1,2-peroxo species at low temperature. It was found that stereochemistry and thermal stability of dioxygen complexes are highly dependent on the steric bulkiness of substituents (R). We have succeeded in structural characterization of a trans-mu-1,2-peroxo species ([Cu ((BnHNCH_2CH_2)_3N)]_2 (O_2)), where benzyl (Bn) groups form a cavity around Cu^<2+>-O_2^<2->-Cu^<2+> moiety, which stabilizes peroxo species. Less

在生物学和催化过程中，O_2的可逆结合和激活中，二铁氧和双氧氧复合物在可逆的结合和激活中起着重要作用。我们开发了各种Diron（II）和DiCopper（I）复合物作为O_2转运蛋白的功能模型，例如Heperthrin（Fe_2）和血胶蛋白（CU_2）和单氧酶，例如甲烷单氧酶（例如甲烷单氧酶）（Fe_2或Cu_n）。只有几个结构上的DIRON DIRON DIRON DIRON DIRON DIRON DIRON DIRON DIRON DIRON DIRON DIRON特征均具有特征性的特征。为了综合Diron-Dioxygen复合物，控制配体环境很重要，该配体环境适用于通过两个铁离子结合的O_2结合，并将Mu-Peroxo物种稳定在不可逆的氧化物上。为此，已经开发了一系列具有吡啶基和咪唑基的二核配体，该配体具有N_6O供体，该供体设置为苯酸酯或烷氧化物桥接组。它们形成五坐标的双核[Fe_2（l）（rco_2）]^<2+>与展览……更多的羧酸酯桥，与O_2反应形成Mu-Peroxo物种。已经发现，这些配合物的不可逆氧化物和二氧化物亲和力高度取决于立体化学和二核配体和桥接羧酸盐的电子供体能力。 Finally We have succeeded in preparation and structural characterization of a cis-mu-1,2-peroxo diron complex which is the first example of a crystallographically characterized diron-dioxygen complex that binds O_2 reversibly at ambient temperature.Dicopper Complexes : A series of copper (I) complexes ([Cu (L)]^+) having tripodal tetradentate ligands （（R_1R_2NCH_2CH_2）_3n：l）合成。研究了这些复合物与O_2的反应性。它们在低温下形成反式MU-1,2-过敏物种。发现二氧化物复合物的立体化学和热稳定性高度依赖于子识别物的空间体积（R）。我们已经成功地进行了反式MU-1,2-过敏物种的结构表征（[Cu（（（BNHNCH_2CH_2）_3N）] _ 2（O_2）），其中苯甲基（BN）组围绕Cu^<2+> -O_2+> - O_2+> -O_2^<2-2-> - > - > - > - > - > - cu^<2+> moeity，稳定型物种，该物种稳定在cu^<2+> - o_2+> - o_2+> - o_2+> - 较少的

项目成果

K.Yamaguchi, M.Suzuki, etc.: "Structures and Catalytic Activities of Carboxylate-bridged Dinickel(II)Complexes as Models for the Metal Center of Urease." Journal of the American Chemical Society. 119. 5752-5753 (1997)

K.Yamaguchi、M.Suzuki 等：“作为脲酶金属中心模型的羧酸桥二镍 (II) 配合物的结构和催化活性”。

Yoshihito Hayashi: "Sythesis,Charaderization,and Reversible Oxygenation of μ-Alkoxo-diiron(II)Complexes with a Dinucleating Ligand,N,N,N',N'-Tetrakis{2-(6-methylpyridyl)methyl}-1,3-diaminopropan-2-olate." J.Am.Chem.Soc.,. 117. 11220-11229 (1995)

Yoshihito Hayashi：“具有双核配体 N,N,N,N-Tetrakis{2-(6-methylpyridyl)methyl}-1 的 μ-Alkoxo-diron(II) 配合物的合成、表征和可逆氧化， 3-二氨基丙烷-2-油酸酯。”J.Am.Chem.Soc.,. 117. 11220-11229 (1995)

H.Sugimoto,M.Suzuki,etc.: "Preparation,Structure and Properties of Some Di (μ-oxo) dirhenium(III,IV),and -(IV,IV)Complexes of Tris(2-pyridylmethyl) amine and 1ts 6-Methy1-2-pyridylmethyl Derivatives." Inorganic Chemistry. 35. 7082-7088 (1996)

H.Sugimoto、M.Suzuki等：“三(2-吡啶甲基)胺与1ts的一些二(μ-氧代)二铼(III,IV)和-(IV,IV)配合物的制备、结构和性能6-甲基1-2-吡啶基甲基衍生物。”无机化学。35. 7082-7088 (1996)

K. Yamaguchi, M.Suzuki, et al.: "Models for Urease : Structures and Reactivities of Carboxylate-Bridged Dinickel(II)Complexes." Journal of Inorganic Biochemistry. 66. 187 (1997)

K. Yamaguchi、M.Suzuki 等人：“脲酶模型：羧酸桥二镍 (II) 复合物的结构和反应性。”

M.Suzuki: "Reactivity of Diiron (II) Complexes with Molecular Oxygen." Journal of Inorganic Biochemistry. 66. 315 (1997)

M.Suzuki：“二铁 (II) 配合物与分子氧的反应性。”