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

由2，6-二甲酰基-4-甲基苯酚与二胺(乙二胺、三甲二胺、四亚甲二胺)[2：2]缩合而成的大环配体的双核MnィイD22ィエD2(II，II)配合物显示出类似于锰过氧化氢酶的活性，能将过氧化氢分解为氧气和水。反应混合物呈深紫色，在530 nm处有特征吸收，v(Mn=O)振动模式约为730 cmィイd1-1ィエd1。冷冻反应混合物显示出具有MnィイD22ィエD2(II，III)特征的EPR信号。已分离到混价的MnィイD22ィエD2(II，III)配合物，其过氧化氢酶活性与相应的双核MnィイD22ィエD2(II，II)配合物相似。推测该络合物为MnィイD22ィエD2(II，II)/MnィイD22ィエD2(II，IV)相互转化分解过氧化氢的分子间反应。大环钴ィイD1IIィエD1MィイD1IIィエD1与‘Co(Sal…)的配合物在大环框架中得到了双核CoィイD1IIィエD1MィイD1IIィエD1配合物[COM(L)(ACO)]CIOィイD24ィエD2和[COM(L)(NCS)]CIOィイD24ィエD2(M=Mn，Fe，Co)，其中LィイD12-ィエD1是由2，6-二甲酰基-4-甲基苯酚2：1：1缩合而成的杂核大环配体，具有两个不同的NィイD22ィエD2OィイD22ィエD2和NィイD23ィエD2OィイD22ィエD2金属结合部位，共享酚氧。Co位于N-ィイ-D22-ィエ-D2O-ィイ-D22-ィエ-D2位上，呈“Co(Salen)”式构型。Co(Salen)位上的氧合受双核结构和相邻的MィイD1IIィエD1离子性质的影响。在醋酸酯络合物中，醋酸桥阻止分子内氧化以提供分子间过氧二聚体{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}.分离出了稳定的过氧络合物M=Co和Mn，并对其进行了晶体结构表征。当不存在额外的桥并且第二个MィイD1IIィエD1容易被氧化时，形成分子内过氧络合物，该络合物很容易通过水解或溶剂分解转化为CoィイD1IIIィエD1MィイD1IIIィエD1物种。类似的CoィイD1IIィエD1CuD1IィイD1IィエD1络合物对氧气非常敏感，通过分子内过氧化络合物很容易转化为CoィイD1IIIィエD1CuD1IIィイィエD1物种。以N(AMME)ィイD22ィエD2OィイD22ィエD2和N(Imine)ィイD22ィエD2OィイD22ィエD2为中心的双核异核配合物以N(胺)ィイD22ィエD2OィイD22ィエD2和N(Imine)ィイD22ィエD2OィイD22ィエD2为金属结合中心合成了新的酚基双核大环化合物。这些配体显示了金属离子的位置选择性，这取决于合成方法、所使用的反离子的性质和大环的空腔大小。单核铜ィイD1IIIィエD1络合物中的金属位于N(亚胺)ィイD22ィエD2OィイD22ィエD2位，通常在氨位容纳第二个MィイD1IIィエD1离子。以Pb-ィイ-D1II-ィエ-D1Cu-ィイ-D1II-ィエ-D-1为前驱体，在铅与M-ィイ-D1II-ィエ-D-1离子的跨金属迁移反应中，将其转化为铜-DNA-D1II-D1M-ィイ-D1II-ィエ-D-1(氨基-铜-M-ィイ-D1II-ィエ-D1)。通过两种合成方法得到了配位异构体。它们具有不同的物理化学性质。较少

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）