JP4016097B2 - Double-helical binuclear complex and its production method - Google Patents
Double-helical binuclear complex and its production method Download PDFInfo
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- JP4016097B2 JP4016097B2 JP2001376645A JP2001376645A JP4016097B2 JP 4016097 B2 JP4016097 B2 JP 4016097B2 JP 2001376645 A JP2001376645 A JP 2001376645A JP 2001376645 A JP2001376645 A JP 2001376645A JP 4016097 B2 JP4016097 B2 JP 4016097B2
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Description
【０００１】
【発明の属する技術分野】
遷移金属は各種の触媒、磁性材料等に利用されており、先端産業に欠かせない金属群と位置づけられている。特に遷移金属の複核錯体は金属-金属間相互作用に起因する特異な性質の発現が期待され、高性能の触媒、磁性材料として注目されている。さらに、分子自身が不斉を持つものは不斉触媒としての機能や偏光素子等の光学的機能も期待される。
【０００２】
【従来の技術】
遷移金属の複核錯体は、金属イオン同士の相互作用により単核錯体にはないユニークな特性を示すことが期待されている。不斉をもつ分子は不斉触媒機能や光学的機能が期待されるが、分子に不斉を導入するためには光学活性部位をもつ原料をつかう必要がある。光学活性部位を用いずに不斉を導入する手段として配位子にらせん構造をもたせる方法も報告されているが（例えばAngew. Chem. Int. Ed. Engl. 31 (1992) 230; Chem. Commun. (1999) 1853.）、一般に構造が複雑になるほど合成は困難になる。
【０００３】
【発明が解決しようとする課題】
遷移金属イオンは一般に４〜６の配位数をもつ。したがって安定な複核錯体を得るためには、複数の配位原子が適切な位置に配置された配位子を合成する必要がある。このような高度に設計された配位子、またその複核錯体を合成するには一般に多段階の複雑な経路が必要である。しかも各段階で満足な収量を得るには余計な副生成物を押さえる必要がある。さらに分子内に不斉を導入するためには光学活性をもつ原料を使う必要があり、コストが増加する。
これを解決する一つの手段が配位子にらせん構造をもたせることであるが、従来のらせん型複核錯体は複数の非環状配位子の集合体でありその安定性には問題がある。また、有機反応の触媒としての用途を考えると、非極性溶媒に溶解したほうが望ましい。この点では従来のイオン性の錯体よりも、金属イオンの電荷がすべて補償された中性錯体の方が適している。
【０００４】
【課題を解決するための手段】
発明者は、２個の配位原子をもつ化合物（ジアルデヒド）２分子と２個の配位原子をもつ化合物（ジアミン）２分子とを縮合させてできる大環状配位子を設計できることがわかった。
この配位子は４個の水酸基と４個の窒素原子をもっており、水酸基が解離することにより4価の負電荷をもつ。したがって２価の遷移金属陽イオン２個と錯形成し中性の錯体を作ることが判った。
化合物１と化合物２を遷移金属塩の共存下で反応させることにより、一分子内に遷移金属イオンを２個有する化合物３で表される大環状二重らせん型複核錯体が得られた。
目的の化合物の構造を確認するためESI-MS, IR, NMR, X線単結晶構造解析を用いて、解析したところ、目的の化合物が得られていることを確認した。
【０００５】
【発明の実施の形態】
本発明において用いるジアルデヒドとしては、1,1-ビス（2’-ヒドロキシー3’-ホルミルベンジル）エチレン等がある。ここにおいてベンゼン環上の置換基は、水素又は低級アルキル基である。
本発明において用いるジアミンとしては、ジエチレングリコールビス（2’-アミノフェニル）エーテル等がある。ここにおいて、エチレングリコール鎖の長さは、適宜調節することができるが、一般式中のｎが１〜５程度が望ましい。
本発明で用いる遷移金属Ｍとしては、Mn, Fe, Co, Ni, Cu, Zn, Pd 等があげられる。
【０００６】
【実施例】
実施例１
次式で表される化合物１を０．５ミリモルと、
【化５】
【化６】
【化７】
実施例２
化合物１を０．５ミリモルと、次式で表される化合物４を０．５ミリモル
【化８】
【化９】
次式で表される化合物６を０．５ミリモルと
【化１０】
【化１１】
実施例１で得られた化合物３をジメチルホルムアミドに溶解しアセトニトリルで希釈してESI-MSを測定したところ、１２３３．１（ｍ／ｚ）にニッケルの複核錯体のピークがナトリウムイオン付加体として観測された。
【００１０】
実施例１で得られた化合物３の単結晶をＸ線回折法により構造解析を行ったところ、配位子部分は大環状の二重らせん構造を持つことが明らかとなった。二重らせん構造はニッケルイオンによって固定されており、各々の分子は結晶中で不斉を持つことがわかった。結晶は右巻のらせんと左巻きのらせんが等量混在したもの、つまりラセミ体であることがわかった。
【発明の効果】
本発明で得られた遷移金属の複核錯体は３次元構造を有する大環状二重らせん型化合物であり、従来の平面型あるいは非環状らせん型に比べて安定である。また不斉をもつ配位子に中心金属が包含された構造になっており、触媒反応など特殊な反応場としてはたらくことが十分に期待される。
クロロホルムやジメチルホルムアミドなど種々の有機溶媒に溶解するため用途も広い。本発明の化合物の生成は、遷移金属イオンを鋳型としたアルデヒドとアミンの自己集合によって引き起こされるため、合成は比較的容易で、大量合成が可能である。[0001]
BACKGROUND OF THE INVENTION
Transition metals are used in various catalysts and magnetic materials, and are positioned as a group of metals indispensable for advanced industries. In particular, transition metal binuclear complexes are expected to exhibit unique properties due to metal-metal interactions, and are attracting attention as high-performance catalysts and magnetic materials. Furthermore, those having asymmetric molecules themselves are expected to have a function as an asymmetric catalyst and an optical function such as a polarizing element.
[0002]
[Prior art]
Transition metal binuclear complexes are expected to exhibit unique properties not found in mononuclear complexes due to the interaction between metal ions. Asymmetric molecules are expected to have an asymmetric catalytic function and an optical function, but in order to introduce asymmetry into the molecule, it is necessary to use a raw material having an optically active site. As a means of introducing asymmetry without using an optically active site, a method of giving a ligand a helical structure has also been reported (for example, Angew. Chem. Int. Ed. Engl. 31 (1992) 230; Chem. Commun. (1999) 1853.) In general, the more complex the structure, the more difficult it is to synthesize.
[0003]
[Problems to be solved by the invention]
Transition metal ions generally have a coordination number of 4-6. Therefore, in order to obtain a stable binuclear complex, it is necessary to synthesize a ligand in which a plurality of coordination atoms are arranged at appropriate positions. In order to synthesize such highly designed ligands and their dinuclear complexes, a multi-step complex route is generally required. In addition, it is necessary to suppress extra by-products in order to obtain a satisfactory yield at each stage. Furthermore, in order to introduce asymmetry into the molecule, it is necessary to use a raw material having optical activity, which increases costs.
One means for solving this is to give the ligand a helical structure, but the conventional helical binuclear complex is an aggregate of a plurality of acyclic ligands, and there is a problem in its stability. Moreover, considering the use as a catalyst for organic reactions, it is desirable to dissolve in a nonpolar solvent. In this respect, a neutral complex in which the charge of all metal ions is compensated is more suitable than a conventional ionic complex.
[0004]
[Means for Solving the Problems]
The inventor found that a macrocyclic ligand formed by condensing two molecules of a compound having two coordination atoms (dialdehyde) and two molecules of a compound having two coordination atoms (diamine) can be designed. It was.
This ligand has four hydroxyl groups and four nitrogen atoms, and has a tetravalent negative charge when the hydroxyl groups are dissociated. Therefore, it was found that a neutral complex was formed by complexing with two divalent transition metal cations.
By reacting compound 1 and compound 2 in the presence of a transition metal salt, a macrocyclic double-helical binuclear complex represented by compound 3 having two transition metal ions in one molecule was obtained.
Analysis using ESI-MS, IR, NMR, and X-ray single crystal structure analysis to confirm the structure of the target compound confirmed that the target compound was obtained.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the dialdehyde used in the present invention include 1,1-bis (2′-hydroxy-3′-formylbenzyl) ethylene. Here, the substituent on the benzene ring is hydrogen or a lower alkyl group.
Examples of the diamine used in the present invention include diethylene glycol bis (2′-aminophenyl) ether. Here, the length of the ethylene glycol chain can be appropriately adjusted, but n in the general formula is preferably about 1 to 5.
Examples of the transition metal M used in the present invention include Mn, Fe, Co, Ni, Cu, Zn, and Pd.
[0006]
【Example】
Example 1
0.5 mmol of compound 1 represented by the following formula:
[Chemical formula 5]
[Chemical 7]
Example 2
0.5 mmol of compound 1 and 0.5 mmol of compound 4 represented by the following formula:
[Chemical 9]
0.5 mmol of compound 6 represented by the following formula:
Embedded image
Compound 3 obtained in Example 1 was dissolved in dimethylformamide, diluted with acetonitrile, and ESI-MS was measured. A peak of a nickel binuclear complex was observed at 1233.1 (m / z) as a sodium ion adduct. It was done.
[0010]
Structural analysis of the single crystal of compound 3 obtained in Example 1 by X-ray diffraction revealed that the ligand part had a macrocyclic double helix structure. The double helix structure was fixed by nickel ions, and each molecule was found to have asymmetry in the crystal. The crystals were found to be a racemic mixture of equal amounts of right-handed and left-handed spirals.
【The invention's effect】
The transition metal binuclear complex obtained in the present invention is a macrocyclic double-helix type compound having a three-dimensional structure, and is more stable than the conventional planar type or acyclic helix type. In addition, it has a structure in which a central metal is included in an asymmetric ligand, and is expected to serve as a special reaction field such as a catalytic reaction.
Since it dissolves in various organic solvents such as chloroform and dimethylformamide, it is widely used. Since the production of the compound of the present invention is caused by the self-assembly of an aldehyde and an amine using a transition metal ion as a template, the synthesis is relatively easy and large-scale synthesis is possible.
Claims (2)
一般式
一般式
で表される大環状二重らせん型複核錯体の製造方法。General formula
General formula
General formula
The manufacturing method of the macrocyclic double helix type binuclear complex represented by these.
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| JP2001376645A JP4016097B2 (en) | 2001-12-11 | 2001-12-11 | Double-helical binuclear complex and its production method |
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|---|---|---|---|
| JP2001376645A JP4016097B2 (en) | 2001-12-11 | 2001-12-11 | Double-helical binuclear complex and its production method |
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| Publication Number | Publication Date |
|---|---|
| JP2003176278A JP2003176278A (en) | 2003-06-24 |
| JP4016097B2 true JP4016097B2 (en) | 2007-12-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190686A (en) * | 2011-01-17 | 2011-09-21 | 天津师范大学 | Binuclear Fe(II) complex of 4-(2-pyridin-)-1,2,4-triazol and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007073562A2 (en) * | 2005-12-20 | 2007-06-28 | Invitrogen Corporation | Fluorescent ion indicators for cadmium and lanthanide ion detection |
-
2001
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190686A (en) * | 2011-01-17 | 2011-09-21 | 天津师范大学 | Binuclear Fe(II) complex of 4-(2-pyridin-)-1,2,4-triazol and application thereof |
| CN102190686B (en) * | 2011-01-17 | 2013-12-11 | 天津师范大学 | Binuclear Fe(II) complex of 4-(2-pyridin-)-1,2,4-triazol and application thereof |
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| Publication number | Publication date |
|---|---|
| JP2003176278A (en) | 2003-06-24 |
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