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

二铁氧和二铜氧配合物在生物和催化过程中对O_2的可逆结合和活化起着重要的作用。我们开发了各种二铁（II）和二铜（I）配合物作为O_2转运蛋白（如血红蛋白（Fe_2）和血蓝蛋白（Cu_2））和单加氧酶（如甲烷单加氧酶（Fe_2或Cu_n））的功能模型。为了合成双铁-双氧配合物，重要的是控制配体环境，使其适合于两个铁离子与O_2的结合，并使μ-过氧物种稳定于不可逆氧化。为此，我们研制了一系列具有空间位阻的吡啶基和咪唑基双核配体，它们的N_6O给体上带有酚盐或醇盐桥联基团。它们形成五配位双核[Fe_2（L）（RCO_2）]^<2+>，配体中含有一个配位原子 ...更多信息 羧酸根桥与O_2反应生成μ-过氧物种。研究发现，这些配合物的不可逆氧化热稳定性和分子氧亲和力高度依赖于双核配体和桥连羧酸盐的立体化学和电子给体能力。最后，我们成功地合成了一个顺式-μ-1，2-过氧二铁配合物，并对其结构进行了表征，该配合物是第一个在室温下可逆结合O_2的二铁-二氧配合物。研究了这些配合物与O_2的反应性。它们在低温下形成trans-mu-1，2-过氧物种。研究发现，双氧配合物的立体化学和热稳定性高度依赖于取代基（R）的空间体积。我们成功地表征了一个反式μ-1，2-过氧物种[Cu（（BnHNCH_2CH_2）_3N）]_2（O_2））的结构，其中苄基（Bn）在Cu^2+&gt;-O_2^<2->-Cu^2+&gt;部分周围形成一个空腔，从而稳定了过氧物种。少

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)

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。”

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。”

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)