Preparation and Spectroscopic Characterization of Unstable Active Oxygen Species

不稳定活性氧的制备及光谱表征

• 批准号: 14350471
• 负责人: FUJISAWA Kiyoshi
• 金额: $ 9.66万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14350471/
• 关键词: transition metal complex; oxygen Complex; spectroscopic characterization; electronic structure; reaction mechanism; model complex; hydroxylation reaction; homogeneous catalytic reaction; 均一触媒反応

1.With hindered pyrazole derivatives, we synthesized novel N2 and N3 ligands. With these ligands, we also discussed the electronic and steric influences on the obtained complexes.2.To obtain mononuclear copper-dioxygen complexes, we explored the most hindered ligand systems. With these ligands, we obtained the superoxo copper(II) complexes and characterized them well3.We observed some differences between Cu-S and Cu-O bond characters.4.Mononuclear iron(II) α-keto and carboxylato complexes were prepared as models for the active sites non-heme iron oxygenases. The oxygenation rate constants of the α-keto acid complexes are faster by 2 orders than those of carboxylato complexes. Therefore, we concluded the key role of the α-keto functionality in oxygen activation by these enzymes.5.We observed the detailed electronic structures of alkylperoxo iron(III) complexes.These results indicate O-O bond hemolytic cleavage in these enzymes.6.We found new olefin polymerization catalysts by use manganese(II) ion.7.We discussed the reaction mechanism of phenol polymerization reaction through"radical controlled"intermediates.8.We also prepared novel Cu(I)-diazene complexes and characterized them well.

1.利用受阻吡唑衍生物，我们合成了新型的N2和N3配体。我们还讨论了电子和空间位阻对配合物的影响。2.为了获得单核铜-二氧配合物，我们探索了最受阻的配体体系。3.观察到Cu-S键和Cu-O键特征的一些差异。4.制备了α-酮基和羧酸基Mono铁（II）配合物作为非血红素铁加氧酶活性中心的模型。α-酮酸配合物的氧化速率常数比羧酸配合物快2个数量级。因此，我们建议，5.对烷基过氧铁（III）配合物的电子结构进行了详细的研究，结果表明这些酶具有O-O键的溶血断裂作用; 6.利用锰（II）离子发现了新的烯烃聚合催化剂; 7.通过“自由基控制”的方法探讨了苯酚聚合反应的机理。8.我们还制备了新型的Cu（I）-二氮烯配合物并对其进行了表征。

项目成果

Spectroscopic Comparison of the five-Coordinate [Cu(SMeIm)(HB(3,5-iPr_2pz)_3] with the four-Coordinate [Cu(SCPh_3)(HB(3,5-iPr_2pz)_3]:

五配位[Cu(SMeIm)(HB(3,5-iPr_2pz)_3]与四配位[Cu(SCPh_3)(HB(3,5-iPr_2pz)_3]的光谱比较：

• 发表时间: 2002
• 期刊: Inorg.Chim.Acta 337
• 作者: L.Basumallick;D.W.Randall;K.Fujisawa;E.I.Solomon
• 通讯作者: E.I.Solomon

P.Chen, D.E.Root, C.Campochiaro, K.Fujisawa, E.I.Solomon: "Spectroscopic and Electronic Structure Studied of the Diamagnetic Side-On Cu^<II>-Superoxo Complex Cu(O_2)[HB{3-R-5-iPrpz)_3] : Antiferromagnetic Coupling vs.Covalent Delocalization"J Am.Chem.Soc.

P.Chen、D.E.Root、C.Campochiaro、K.Fujisawa、E.I.Solomon：“抗磁性侧面 Cu^<II>-Superoxo 络合物 Cu(O_2)[HB{3-R-5] 的光谱和电子结构研究

Synthetic Models for Active Sites of Reduced Blue Copper Proteins : Minimal Geometric Change between Two Oxidation States for Fast Self-exchange Rate Constants

还原蓝铜蛋白活性位点的合成模型：快速自交换速率常数的两个氧化态之间的最小几何变化

• 发表时间: 2004
• 期刊: Inorg.Chem.Commun. 7
• 作者: K.Fujisawa;K.Fujita;N.Kitajima;Y.Mastunaga;Y.Miyashita;K.Okamoto
• 通讯作者: K.Okamoto

Spectroscopic and Electronic Structure Studies of the Diamagnetic Side-On Cu^<II>-Superoxo Complex Cu(O_2)[HB{3-R-5-Prpz)_3] : Antiferromagnetic Coupling versus Covalent Delocalization.

反磁性侧向 Cu^<II>-超氧配合物 Cu(O_2)[HB{3-R-5-Prpz)_3] 的光谱和电子结构研究：反铁磁耦合与共价离域。

• 发表时间: 2003
• 期刊: J.Am.Chem.Soc. 125
• 作者: P.Chen;D.E.Root;C.Campochiaro;K.Fujisawa;E.I.Solomon
• 通讯作者: E.I.Solomon

K.Fujisawa, T.Ono, H.Aoki, Y.Ishikawa, Y.Miyashita, K.Okamoto, H.Nakazawa, H.Higashimura: "Copper(II) Complexes with a Novel Tris(3,5-diisopropyl-1-pyrazolyl)methane Ligand"Inorg.Chem.Commun.. 7. 330-332 (2004)

K.Fujisawa、T.Ono、H.Aoki、Y.Ishikawa、Y.Miyashita、K.Okamoto、H.Nakazawa、H.Higashimura：“具有新型 Tris(3,5-二异丙基-1) 的铜 (II) 配合物