Characteristics and Functions of Dinuclear Complexes in Unusual Oxidation States

异常氧化态双核配合物的特征和功能

• 批准号: 09440231
• 负责人: OKAWA Hisashi
• 金额: $ 8.19万
• 依托单位: KYUSHU 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 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440231/
• 关键词: Macrocyclic ligand; Dinuclear complex; Mixed-valence complex; Unusual oxidation state; Oxygenation; Heterodinuclear complex; Catalase-like function; Peroxo complex; 酵素錯体; ベルオキソ錯体; スーパーオキソ錯体; コンバートメント配位子; 鋳型反応; ヘテロ二核錯体

1. Macrocyclic Dinuclear Mn Complexes as Functional Mn CatalasesDinuclear MnィイD22ィエD2(II, II) complexes of Macrocyclic ligands derived from the [2 : 2] condensation between 2, 6-diformyl-4-methylphenol and diamine (ethylenediamine, trimethylenediamine, tetramethylenediamine) showed a Mn-catalase like activity to disproprtionate hydrogen peroxide into dioxygen and water. The reaction mixture assumed a deep purple color and showed a characteric absorption at 530 nm having v(Mn=O) vibration modes of ca. 730 cmィイD1-1ィエD1 separation. A frozen reaction mixture showed EPR signals characteristic of MnィイD22ィエD2(II, III). Mixed-valence MnィイD22ィエD2(II, III) complexes have been isolated that a catalase-like activity similar to that of the corresponding dinuclear MnィイD22ィエD2(II, II) complex. An intermolecular of hydrogen peroxide decomposition by the interconversion of MnィイD22ィエD2(II, II)/MnィイD22ィエD2(II, IV) is inferred for the complexes.2. Macrocyclic CoィイD1IIィエD1MィイD1IIィエD1 Complexes with 'Co(sal … More en)' in A Macrocyclic FrameworkDinuclear CoィイD1IIィエD1MィイD1IIィエD1 Complexes [CoM(L)(AcO)]CIOィイD24ィエD2 and [CoM(L)(NCS)]CIOィイD24ィエD2 (M=Mn, Fe, Co) have been obtained where LィイD12-ィエD1 is a heterodinucleating macrocyclic ligand derived by the 2 : 1 : 1 condensation of 2, 6-diformyl-4-methylphenol, ethylenediamine and diethylenetriamine and has two dissimilar NィイD22ィエD2OィイD22ィエD2 and NィイD23ィエD2OィイD22ィエD2 metal-binding sites sharing the phenolic oxygens. The Co resides in the NィイD22ィエD2OィイD22ィエD2 site and assumed a 'Co(salen)'-like geometry. The oxygenation at the 'Co(salen)' site is influenced by the dinuclear core structure and the nature of the adjacent MィイD1IIィエD1 ion. In the acetate complexes the acetate bridge prohibits an intramolecular oxygenation to provide an intermolecular peroxo dimer, {MィイD1IIィエD1CoィイD1IIIィエD1-O-O-CoィイD1IIIィエD1MィイD1IIィエD1}. Stable peroxo complexes have been isolated for M=Co and Mn and crystallographycally characterized. When no additional bridge exists and the second MィイD1IIィエD1 is susceptible to oxydation, an intramolecular peroxo complex is formed that is readily converted into a CoィイD1IIIィエD1MィイD1IIIィエD1 species by hydrolysis or solvolysis. An analogous CoィイD1IIィエD1CuィイD1IィエD1 complex was very sensitive to dioxygen and readily converted into a CoィイD1IIIィエD1CuィイD1IIィエD1 species through an intramolecular peroxide complex..3. Heterodinuclear Complexes of Dinucleating with N(anime)ィイD22ィエD2OィイD22ィエD2 and N(imine)ィイD22ィエD2OィイD22ィエD2 SitesNew phneol-based dinucleating macrocycles with N(amine)ィイD22ィエD2OィイD22ィエD2 and N(imine)ィイD22ィエD2OィイD22ィエD2 metal-binding sites have been developed for the study of heterodinuclear complexes. The ligands show site-selectivity of metal ions depending upon a synthetic method, the nature of the counter ion used and the cavity sizes of the macrocycles. The mononuclear CuィイD1IIIィエD1 complex has the metal in the N(imine)ィイD22ィエD2OィイD22ィエD2 site and generally accommodates the second MィイD1IIィエD1 ion in the aminic site. PbィイD1IIィエD1CuィイD1IIィエD1 complexes with Pb in the aminic site and Cu in the iminic site have been derived as precursors which were converted into CuィイD1IIィエD1MィイD1IIィエD1 complexes (with Cu in the aminic site and M in the iminic site) in the transmetallation of the Pb for MィイD1IIィエD1 ion. Coordination-position isomers have been derived by the two synthetic methods. They were characterized by different physicochemical properties. Less

1.大环双核锰配合物作为功能性锰过氧化氢酶2，6-二甲酰基-4-甲基苯酚与乙二胺、三亚甲基二胺、四亚甲基二胺[2：2]缩合生成的双核锰配合物D22-D22（II，II）具有锰过氧化氢酶样活性，能将过氧化氢分解为分子氧和水。反应混合物呈现深紫色，在530 nm处显示特征吸收，其v（Mn=O）振动模式为约1.5。730 cm宽D1-1宽D1间隔。冷冻的反应混合物显示出Mn（OH）2 D22-D2（II，III）的EPR信号特征。已分离到混合价Mn D22 D2（II，III）配合物，其过氧化氢酶样活性类似于相应的双核Mn D22 D2（II，II）配合物。推测配合物分子间的过氧化氢分解是通过Mn D22 D2（II，II）/Mn D22 D2（II，IV）的相互转化进行的.大环Co（Ⅲ）D1 Ⅱ、D1 M、D1 Ⅱ、D1与Co（Ⅲ）的配合物 ...更多信息 大环框架中的双核Co（Ⅱ）D1 Ⅱ配合物[CoM（L）（AcO）]CIO（Ⅱ）D24 D2和[CoM（L）（NCS）]CIO（Ⅱ）D24 D2（M=Mn，Fe，Co），其中L_2D_12-L_2D_1是由2：1：1缩合，并具有两个不同的金属结合位点，N-二甲酰基-4-甲基苯酚，乙二胺和二亚乙基三胺，N-二甲酰基-4-甲基苯酚，乙二胺和N-二甲酰基-4-甲基苯酚，N-二甲酰基-4-甲基苯酚，乙二胺和二亚乙基三胺。Co存在于N_（22）O在'Co（salen）'站点的氧化作用受到双核核心结构和相邻的M D1 II D1离子的性质的影响。在醋酸盐络合物中，醋酸盐桥阻止了分子内的氧化作用，形成了分子间的过氧二聚体，{M D1 II D1 Co D1 III D1-O-O-Co D1 III D1 M D1 II D1}。稳定的过氧配合物已被分离为M=Co和Mn和crystallographycally其特征在于。当没有额外的桥存在和第二个M D1 II D1是易受氧化，形成分子内过氧复合物，很容易转化为Co D1 III D1 M D1 III D1物种通过水解或溶剂分解。一个类似的Co D1 II D1 Cu D1 I D1配合物对分子氧非常敏感，并且容易通过分子内过氧化物配合物转化为Co D1 III D1 Cu D1 II D1物种。3.含N（胺）取代D22取代D22取代D2 O取代D22取代D22取代D2和N（亚胺）取代D22取代D22取代D2 O取代D22取代D2的双核异双核配合物的研究开发了含N（胺）取代D22取代D22取代D2 O取代D22取代D2和N（亚胺）取代D22取代D22取代D2金属结合位点的新型酚基双核大环化合物。配体显示出金属离子的位点选择性，这取决于合成方法、所用抗衡离子的性质和大环的空腔尺寸。单核的Cu D1 III D1络合物在N（亚胺）D22 D2 O D22 D2位点具有金属，并且通常在胺位点容纳第二个M D1 III D1离子。以Pb的氨基位和Cu的亚胺位为前体的Pb Ⅱ D1 Ⅱ D1 Cu Ⅱ D1 Ⅱ D1配合物为前体，在Pb对M Ⅱ D1 Ⅱ D1离子的转移过程中，转化为Cu Ⅱ D1 Ⅱ D1 Ⅱ D1配合物（Cu在氨基位，M在亚胺位）。用这两种合成方法得到了配位异构体。它们的特点是不同的物理化学性质。少

项目成果

H. Furutachi: "Reversible Oxygenation of a u-Acetato-di(u-phenoxo)dicobalt(II) Core Complex and Crystal Structure of Its Oxygenated Complex"Chem. Lett.. 779-780 (1998)

H. Furutachi：“u-乙酰基-二（u-苯氧）二钴（II）核心配合物的可逆氧化及其含氧配合物的晶体结构”Chem。

K. Takahashi, J. Shimada, M. Itoh, Y. Fuchida, and H. Okawa: "Synthesis and Characterization of Triple-decker Sandwich Dinuclear La(III) and Lu(III) Complexes of Octabutoxyphthalocyanine"Chem. Lett.. (No. 2). 173-174 (1998)

K. Takahashi、J. Shimada、M. Itoh、Y. Fuchida 和 H. Okawa：“八丁氧基酞菁的三层夹心双核 La(III) 和 Lu(III) 配合物的合成和表征”Chem。

S. Yamanaka, H. Okawa, D. E. Fenton, and A. B. P. Lever: "Tetracopper Assembly Complexes Comprised of One Dimetallic and Two Monometallic Auxiliaries : Intramolecular Electron-Transfer Relevant to Multicopper Oxidases"Inorg. Chem.. 38(No. 8). 1825-1830 (1

S. Yamanaka、H. Okawa、D. E. Fenton 和 A. B. P. Lever：“由一种二金属和两种单金属辅助剂组成的四铜组装复合物：与多铜氧化酶相关的分子内电子转移”Inorg。

E,Asato: "New Pyridine-modified Macrocycle and Its Ability to Encapsulate Four Divalent Meta Ions[Ni(II),Mu(II),Zn(II)]into the Ring"Chemistry Letters. 1999・7. 647-648 (1999)

E，Asato：“新型吡啶修饰大环及其将四种二价金属离子[Ni(II)、Mu(II)、Zn(II)]封装到环中的能力”《化学快报》1999・7。 1999）

H.Furutachi: "A Rare μ^3η1,η1 Peroxo Bridge between Two Co^<III> Pb^<II> Dinuclear Units and Hydrolytic Conversion into A Hydroxo-bridged Co^<III> Pb^<II> Complex"Chemistry Letters. 1999・8. 763-764 (1999)

H.Furutachi：“两个 Co^<III> Pb^<II> 双核单元之间的罕见 μ^3η1,η1 过氧桥和水解转化为羟基桥联的 Co^<III> Pb^<II> 络合物”化学快报1999・8。763-764（1999）