Metal Ion Collection Systems Based on the Ligned Basicity Change on Redox Reactions of Some Metal Complexes

基于某些金属配合物氧化还原反应的碱度变化的金属离子收集系统

• 批准号: 09554037
• 负责人: SASAKI Yoichi
• 金额: $ 7.1万
• 依托单位: HOKKAIDO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-09554037/
• 关键词: Metal-Metal Bond; Transition Metal Elements; Functional Electrode; Enzyme Model Complexes; Metal Cluster Complexes; Redox Reactions; Electrode Reactions; Catalytic Reactions

Basicity of oxide bridge of dinuclear complexes changes remarkably with the change in the oxidation states of the metal ions. It is thus possible to control the interaction of the oxide bridge with various Lewis acids like metal ions by changing the metal oxidation states. This work aimed at preparing the electrodes with surface self-assembled monolayers of such metal complexes, and use them as reversible metal-ion binder and to establish the method for the step-wise construction of metal-complex oligomers. The results are summarized as follows.(1)Methods to construct Au self-assembled monolayers of polynuclear metal complexes have been established by using(i)mixed monolayers with alkyl sulfide and(ii)hydrogen bonding between the chains which contain C-CO-NH-groups.(2)Protoncoupled electron transfer behavior of the oxo-bridged biruthenium complexes on gold surface have been quantitatively investigated. Diiron alnalaogs which are considered as models of biological diiron centers and are unstable towards redox reactions in solution, have been successfully studied in terms of pH-potential profiles over pH range of 1 and 12. The pKa values of the oxidized and reduced forms have been estimated for the first time for the model Fe-O-Fe complexes.(3)Coupled redox reactions have been studied quantitatively with Lewis acids other than proton for the first time. Thus, for example, interaction of Al^<3+> ions at the oxide bridge is more sensitive to the metal ion oxidation states than protons.(4)Step-wise oligomerization of the trinuclear oxo-centered Ru complexes on Au electrode has been established by controlling the metal oxidation state. The method is promising in contructing various supramolecular assemblies on electrode surfaces.

随着金属离子氧化态的变化，双核配合物的氧化桥碱度发生显著变化。因此，可以通过改变金属氧化状态来控制氧化桥与各种路易斯酸(如金属离子)的相互作用。本工作旨在制备这种金属络合物的表面自组装单分子膜电极，并将其作为可逆的金属-离子结合剂，建立逐步构建金属-络合物齐聚物的方法。主要结果如下：(1)利用(I)烷基硫化物的混合单分子膜和(Ii)含C-CO-NH-基团的链之间的氢键，建立了金多核金属络合物自组装单分子膜的构筑方法。(2)定量研究了氧桥联双金属络合物在金表面的质子耦合电子转移行为。本文成功地研究了溶液中对氧化还原反应不稳定的生物双铁中心模型DiIron alnalog在pH为1和12范围内的pH-电势分布。首次估算了模型Fe-O-Fe络合物的氧化和还原形式的pKa值。(3)首次定量研究了除质子以外的Lewis酸的氧化还原偶联反应。因此，例如，Al^&lt；3+&gt；离子在氧化桥上的相互作用对金属离子的氧化态比质子更敏感。(4)通过控制金属氧化态，实现了三核氧中心Ru络合物在金电极上的分步齐聚。该方法在电极表面构建各种超分子组装材料方面具有广阔的应用前景。

项目成果

Pu Quan, et al.: "Chiral Molecular Patterns of Self-assembled Ion Pairs Composed of (R, S), (S)-16-Methyloctadecanoic Acid and 4, 4'-Bipyridine."Chemical Communications. No.22. 2021-2022 (2000)

Pu Quan 等人：“由 (R, S), (S)-16-甲基十八烷酸和 4, 4-联吡啶组成的自组装离子对的手性分子模式。”化学通讯。

Pu Qian: "Self-Assembly of Alkyl Substituted Schiff Base and Its Cu) II) Complex Observed on Solution-Graphite Interface by Scanning Tunneling Microscopy"Chemistry Letters. No.11. 1118-1119 (2000)

濮谦：“通过扫描隧道显微镜在溶液-石墨界面上观察烷基取代希夫碱及其Cu)II)配合物的自组装”化学快报。

Tomohiko Inomata: "Self-Assembled Monolayers of Non-Heme Diiron(III) Model Complexes on Au(111) Electrode : Synthesis and Proton-Coupled Redox Behavior in Water"Chem. Lett.. No.10. 1097-1098 (1999)

Tomohiko Inomata：“Au(111) 电极上非血红素二铁 (III) 模型复合物的自组装单层：合成和水中质子耦合的氧化还原行为”Chem。

Masaaki Abe: "Lewis Acid Trifluoroboran Coordimation to trans-Dioxorhenium(V)Moiety:Structural and Spectroscopic Characterization of trans-[Re(O)(OBF_3)(1-Meim)_4](BF_4)(Meim=1-methylimidazole)." Chemistry Letters. No.10. 1073-1074 (1997)

Masaaki Abe：“刘易斯酸三氟硼烷与反式二氧铼(V)部分的配位：反式-[Re(O)(OBF_3)(1-Meim)_4](BF_4)(Meim=1-甲基咪唑)的结构和光谱表征。

T.Fukumoto: "Preparation and Properties of a Series of the(μ-Oxo)di(μ-acetato)diruthenium(III) Complexes. [Ru_2(μ-O)(μ-CH_3COO)_2(Pyridine)_4(L)_2]^<2+> and [Ru_2(μ-O)(μ-CH_3COO)_2(AA)_2(L)_2]^<2+>, where AA is 2,2'-Bipyridine or 1,10-Phenanthroline, and

T.Fukumoto：“一系列(μ-Oxo)di(μ-acetato)二钌(III)络合物的制备和性质。[Ru_2(μ-O)(μ-CH_3COO)_2(吡啶)_4(L) _2]^<2+> 和 [Ru_2(μ-O)(μ-CH_3COO)_2(AA)_2(L)_2]^<2+>，其中 AA 为 2,2-联吡啶或 1,10-菲咯啉，和