Development of Dinuclear and Multinuclear Transition Metal Complexes with Novel Properties

具有新性能的双核和多核过渡金属配合物的开发

• 批准号: 02640471
• 负责人: UEHARA Akira
• 金额: $ 1.28万
• 依托单位: Faculgy of Science, Kanazawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640471/
• 关键词: Dinuclear Cobalt Complexes; Dinuclear Iron Complexes; Dinuclear Manganese Complexes; Tetranuclear Manganese Complexes; Molecular Oxygen Complexes; Solid-phase Syntheses; Magnetic Interaction; 集積型金属錯体; 二核クロム錯体

(1) Design and Preparation of Tetranuclear Manganese Complexes for the Models of Manganese Clusters Involved in Oxygen Evolving Center (OEC) in Photo-system II : Novel tetranuclear manganese complexes with 1, 3-Bis[bis (2-pyridyl-methyl) amino]-2-propanol (Htpdp) and 1, 5-Bis[bis (2-pyridylmethyl) amino]-3-pentanol (Htmdp) were newly prepared and their structures were clarified. The complexes are characteristic of having two di (mu- oxo) Mn_2 (III, IV) units. Especially, the latter tmdp complex contains two water molecules in close proximity to the di (mu-oxo) Mn_2 (III, IV) units. Therefore, the complex is worth noting sa effective model for the tetranuclear manganese clusters involved in OEC.(2) Preparation of Dinuclear Cobalt and Iron Complexes Which Reversibly React with Molecular Oxygen : The dinuclear cobalt (II, II) complex [Co_2 (tpdp or tmdp) (CH_3COO)]^<2+> was newly prepared. The complex was found to react with molecular oxygen to form mu -peroxo complex. In addition, the dinuclear iron (II, II) complex containing N, N, N', N'-Tetrakis[2-(6-methylpyridyl) methyl]-1, 3-diamino-propane-2-ol (6Me-Htpdp) was newly prepared. The complex is very interesting in that it reversibly reacts with molecular oxygen at -20ﾟC. We are trying to prepare the oxygen complex which can be isolated even under ambient conditions.(3) Thermal Reactions of Solid Metal Complexes : For the construction of novel multinuclear metal complexes, a new solid-phase synthetic method must be developed in addition to usual liquid-phase method. To do this, the solid-phase thermal reactions of various metal complexes should be fully understood. The structural changes (especially isomerization) of a variety of nickel (II), cobalt(III), and chromium (III) complexes were investigated. The results obtained in the present study will give fundamental data for the development of a new synthetic method.

(1) 光系统II中参与氧放出中心(OEC)的锰簇模型的四核锰配合物的设计和制备：具有1, 3-双[双(2-吡啶基-甲基)氨基]-2-丙醇(Htpdp)和1, 5-双[双(2-吡啶基甲基)的新型四核锰配合物 新制备了氨基]-3-戊醇(Htmdp)并阐明了其结构。该配合物的特点是具有两个二(mu-oxo) Mn_2 (III, IV) 单元。特别是，后一个 tmdp 复合物包含两个靠近 di (mu-oxo) Mn_2 (III, IV) 单元的水分子。因此，该配合物作为参与OEC的四核锰簇的有效模型是值得注意的。(2)与分子氧可逆反应的双核钴铁配合物的制备：新制备了双核钴(II,II)配合物[Co_2(tpdp或tmdp)(CH_3COO)]^<2+>。发现该络合物与分子氧反应形成μ-过氧络合物。此外，新制备了含有N,N,N',N'-四[2-(6-甲基吡啶基)甲基]-1,3-二氨基-丙烷-2-醇(6Me-Htpdp)的双核铁(II,II)络合物。该配合物非常有趣，因为它在-20℃下与分子氧发生可逆反应。我们正在尝试制备即使在环境条件下也可以分离的氧配合物。(3)固体金属配合物的热反应：为了构建新型多核金属配合物，除了通常的液相方法之外，还必须开发新的固相合成方法。为此，应充分了解各种金属配合物的固相热反应。研究了各种镍 (II)、钴 (III) 和铬 (III) 配合物的结构变化（特别是异构化）。本研究获得的结果将为开发新的合成方法提供基础数据。

项目成果

Y.Ihara,Y.Satake,M.Suzuki,and A.Uehara: "cis-trans Isometism among the Octahedral DIaqua(N,N- or N,N'-Dialkylethylenediamine)nickel(II) Complexes and Their Thermal Reaction Products" Bull.Chem.Soc.Jpn.64. 3647-3652 (1991)

Y.Ihara、Y.Satake、M.Suzuki 和 A.Uehara：“八面体 DIaqua（N,N- 或 N,N-二烷基乙二胺）镍 (II) 配合物及其热反应产物中的顺反异构现象”

E. Itoh, K. Yamamoto, M. Funato, M. Suzuki, and A. Uehara.: "Preparation of Chromium (III) Complexes with a Series of Tetraazacycloalkanes, [12]aneN_4 to [16]aneN_4, and Solid-state Thermal Isomerization of cis-[CrCl_2-([15]- or [16]aneN_4) ]^+." Thermoch

E. Itoh、K. Yamamoto、M. Funato、M. Suzuki 和 A. Uehara.：“用一系列四氮杂环烷烃、[12]aneN_4 至 [16]aneN_4 和固态制备铬 (III) 配合物

Y.Hayashi,M.Suzuki,A.Uehara,Y.Mizutani,and T.kitagawa: "(μーAlkoxo)ーdiiron(II,II)Complexes of N,N,N',N'ーTetrakis[2ー(6ーmethylpyridyl)methyl]ー1,3ーdiaminopropaneー2ーolate and the Reversible Formation of the O_2ーAdduct" Chem.Lett.91-94 (1992)

Y.Hayashi、M.Suzuki、A.Uehara、Y.Mizutani 和 T.kitakawa：“(μーAlkoxo)ーdiiron(II,II)N,N,N,NーTetrakis 配合物[2ー(6-甲基吡啶基)甲基]-1,3-二氨基丙烷-2-油酸酯和 O_2-加合物的可逆形成”Chem.Lett.91-94 (1992)

E.Itoh,M.Suzuki,and A.Uehara: "Thermal Isomerization of cis-〔CrCl_2(〔15〕aneN_4)〕SCN in the Soli State" Thermochim.Acta.

E.Itoh、M.Suzuki 和 A.Uehara：“Soli 状态下顺式-[CrCl_2([15]aneN_4)]SCN 的热异构化”Thermochim.Acta。

M.Suzuki,T.Sugisawa,and A.Uehara: "Dinuclear Cobalt(II) Complexes Containing 1,3ー(or 1,5ー)Bis[bis(2ーpyridylmethyl)amino]ー2ーpropanolate(or ー3ーpentanolate):Preparation and Reaction with Molecular Oxygen." Bull.Chem.Soc.Jpn.63. 1115-1120 (1990)

M.Suzuki、T.Sugisawa 和 A.Uehara：“含有 1,3－（或 1,5－）双[双（2－吡啶甲基）氨基]－2－丙醇盐（或 -3）的双核钴（II）配合物-戊醇）：与分子氧的制备和反应。” Bull.Chem.Soc.Jpn.63. 1115-1120 (1990)