Investigations of dioxygen activation mechanisms by dimetal complexes

双金属配合物双氧活化机制的研究

• 批准号: 11228202
• 负责人: SUZUKI Masatatsu
• 金额: $ 38.14万
• 依托单位: Kanazawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11228202/
• 关键词: Dioxygen active species; Oxidation reaction; Dioxygen activation; Nickel complexes; Iron complexes; Copper complexes; High valent metal complexes; Crystal structures; モノオキシゲナーゼ; パーオキソ錯体; 酸素-酸素結合の再生; 酸素-酸素結合の開裂; ヒドロペルオキソ錯体; 二核銅(III)オキソ錯体; 酵素活

<Reversible four electron redox conversion of dioxygen by copper complexes > A series of copper(I) complexes ([Cu(L)]^+) having tripodal tetradentate ligands (L) was synthesized and reactivity of their complexes with O_2 was investigated. Reaction of copper(I) complexes ([Cu(L)]^+ generated bis(μ-oxo)dicopper(III) complexes, which showed reversible conversion to copper(I) complexes by bubbling of N_2. Furthermore, it was also found that bis(μ-oxo)dicopper(III) complexes have monooxygenase activity for the supporting ligands. Reactivity can be modulated by stereochemical electronic effect of the supporting ligands<Reaction intermediates of nickel complexes having a variety of dioxygen active species formed by the reaction with H_2O_2> Reaction of a bis(μ-hydroxo)Ni(II)_2 having a series of tetradentate tripodal ligands having methyl substituents with H_2O_2 at low temperature resulted in a successive formation a bis(μ-oxo)Ni(III)_2 a bis(μ-superoxo)Ni(II)_2, and a bis(μ-alkylperoxo)Ni(II)_2 complexes as the intermediates for the conversion of a methyl substituent of ligands to carboxylate and alkoxide ligands<Reversible O-O bond cleavage and formation of a peroxo group of an iron(III) complex having a peroxycarbonate> A peroxcarbonate iron(III) complex ([Fe(qn)_2(O_2C(O)O)]^-(1)) was synthesized. The complex is stable at -35℃ in acetonitrile, whereas it decomposes at 20℃. Decomposition of an ^<18>O-labeled [Fe(qn)_2(^<18>O-^<18>OC(O)O)]^-complex (1-^<18>O-^<18>O) at 20℃ in acetonitrile was investigated by resonace Raman and ESI-MS spectroscopies. They revealed that the ^<18>O-^<18>O of the peroxocarboante ligand is converted through ^<16>O-^<18>OC(O)O and ^<18>O-^<16>OC(O)O to ^<16>O-^<16>OC(O)O during thermal decomposition. This is the first example which showed reversible O-O bond cleavage and formation for iron complexes

合成了一系列具有三足四齿配体(L)的铜(I)配合物（[Cu(L)]^+），并研究了它们与O_2的反应性。铜(I)配合物（[Cu(L)]^+）反应生成双（μ-氧）二铜（III）配合物，在氮气鼓泡作用下可逆转化为铜(I)配合物。此外，还发现双（μ-氧）二铜（III）配合物对支撑配体具有单加氧酶活性。反应活性可通过支撑配体的立体化学电子效应来调节：与H_2O_2反应形成多种双氧活性的镍配合物的反应中间体>双（μ-羟基）Ni(II)_2在低温下与H_2O_2具有一系列甲基取代的四齿三脚配体反应，形成双（μ-氧）Ni(III)_2和双（μ-超氧）Ni(II)_2。并合成了一种双（μ-烷基过氧）Ni(II)_2配合物作为中间体，使配体的甲基取代基转化为羧酸盐和烷氧基配体。该配合物在乙腈中-35℃稳定，在20℃分解。用共振拉曼光谱和ESI-MS光谱研究了在乙腈中，在20℃下，Fe(qn)_2(^<18>O-^<18>OC(O)O)]^-配合物（1-^<18>O-^< 18>o）的分解。结果表明，过氧碳酸配体的^<18> -^<18>O在热分解过程中通过^<16>O-^<18>OC(O)O和^<18>O-^<16>OC(O)O转化为^<16>O-^<16>OC(O)O。这是第一个证明铁配合物可逆O-O键裂解和形成的例子

项目成果

K.Yamaguchi, M.Suzuki, et al.: "Hydrolysis of Phosphodiester with Hydroxo- or Carboxylate-bridged Dinuclear Ni(II) and Cu(II) Complexes"Journal of Chemical Society, Chemical Communication. 375-376 (2001)

K.Yamaguchi、M.Suzuki 等人：“用羟基或羧酸桥联的双核 Ni(II) 和 Cu(II) 配合物水解磷酸二酯”，化学会杂志，化学通讯。

H.Hayashi, M.Suzuki, et al.: "Modulation of the Copper-Dioxygen Reactivity by Stereochemical Effect of Tetradentate Tripodal Ligends"Chemistry Letters. 416-417 (2002)

H.Hayashi、M.Suzuki 等人：“通过四齿三足配体的立体化学效应调节铜-分子氧反应性”化学快报。

Chow, J., Suzuki, M.et al.: "Formation and Characterization of a Bis(μ-allrylperoxo)dinickel(II) Complex as a Reaction Intermediate for Oxidation of Methyl Getup ofMe_2-tpa Ligand to Carboxyl ate and Alkoxide Ligands"Angewandte Chemie International Editio

Chow, J., Suzuki, M.等人：“双(μ-烯丙基过氧)二镍(II)络合物作为Me_2-tpa配体甲基氧化成羧酸和醇盐配体的反应中间体的形成和表征”应用化学国际社论

H.Hayashi, M.Suzuki: "Modulation of the Copper-Dioxygen Reactivity by Stereochemical Effect of Tetradentate Tripodal Ligands"Chemistry Letters. 416-417 (2002)

H.Hayashi，M.Suzuki：“通过四齿三足配体的立体化学效应调节铜-双氧反应性”化学快报。

Kodera, M., Suzuki, M.: "Synthesis, Structure, and Greatly Improved Reversible O_2 Binding in a Structurally Modulated μ-η^2 : η^2-Peroxodicopper(II) Complex with Room-Temperature Stability"Angewandte Chemie International Edition. 43. 334-337 (2004)

Kodera, M., Suzuki, M.：“具有室温稳定性的结构调制 μ-η^2 : η^2-Peroxodicopper(II) 复合物的合成、结构和大大改进的可逆 O_2 结合”Angewandte Chemie 国际版. 43. 334-337 (2004)