JPH0673060A - New binuclear manganese=porphyrin complex and electrode modified therwith and method for electrochemical reaction using the electrode - Google Patents
New binuclear manganese=porphyrin complex and electrode modified therwith and method for electrochemical reaction using the electrodeInfo
- Publication number
- JPH0673060A JPH0673060A JP92253645A JP25364592A JPH0673060A JP H0673060 A JPH0673060 A JP H0673060A JP 92253645 A JP92253645 A JP 92253645A JP 25364592 A JP25364592 A JP 25364592A JP H0673060 A JPH0673060 A JP H0673060A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- manganese
- porphyrin
- reaction
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有望なエネルギー源と
考えられている水素を水の電気分解によって効率的に生
産し、あるいはより効率的な有用化学物質の電気化学的
生産反応系の構築に極めて有効な化学修飾電極、および
その反応中心となる新規な二核マンガン＝ポルフィリン
錯体に関する。FIELD OF THE INVENTION The present invention efficiently produces hydrogen, which is considered as a promising energy source, by electrolysis of water, or constructs a more efficient electrochemical production reaction system of useful chemical substances. The present invention relates to a chemically modified electrode, which is extremely effective for use in the above, and a novel binuclear manganese porphyrin complex which is a reaction center thereof.
【０００２】[0002]
【従来の技術】植物の光合成において極めて効率的に水
を４電子酸化させ、１分子の酸素と４つのプロトンを発
生させる反応触媒系は４核マンガン錯体を活性中心とす
るものであることが知られている〔R.Hoffmann,et al.,
J. Am. Chem. Soc., 114, p4374 (1992).〕。この触媒
の機能を解明し、あるいは利用する目的で種々の金属錯
体が合成され検討されたが、安定な触媒であり、かつ水
を酸化することにより酸素を発生させることができる多
核マンガン錯体触媒は、発明者の知る限り、今だ開発さ
れていない。2. Description of the Related Art It is known that a reaction catalyst system that highly efficiently 4-electron-oxidizes water to generate one molecule of oxygen and four protons in a photosynthesis of a plant has a tetranuclear manganese complex as an active center. (R. Hoffmann, et al.,
J. Am. Chem. Soc., 114 , p4374 (1992).]. Various metal complexes have been synthesized and studied for the purpose of clarifying or utilizing the function of this catalyst, but a polynuclear manganese complex catalyst that is a stable catalyst and that can generate oxygen by oxidizing water is As far as the inventor knows, it has not been developed yet.
【０００３】ところで、近年きれいなエネルギー源とし
て注目されている水素を生産する方法として水の電気
分解、多段化学反応を利用した熱化学法、高温直接
分解法、太陽光水分解法が検討されている〔「資源エ
ネルギー年鑑 １９９３」資源エネルギー庁監修、通産
資料調査会刊、平成４年、pp812；「エレクトロキャタ
リシスの展望と応用」喜多英明編著、アイピーシー社
刊、平成２年；「技術予測シリーズ第２巻・エネルギー
編、１１章水素エネルギーシステム」太田時男、日本ビ
ジネスレポ−ト社刊、昭和６０年、pp131〕。このう
ち、特に水の電気分解を用いて水素を生産する方法がエ
ネルギーが入手しやすい有望な方法として種々の検討が
なされている。しかし、この電気分解においては電極に
おける過電圧が電解効率を低下させてしまい、電気エネ
ルギーを効率的に化学エネルギーに変換することを妨げ
る一要因となっている。そのため電気分解法は特にエネ
ルギー源としての水素の生産方法としての実用性をもつ
には今だ到っていない。By the way, as a method for producing hydrogen, which has been attracting attention as a clean energy source in recent years, electrolysis of water, thermochemical method utilizing multi-step chemical reaction, high temperature direct decomposition method, and solar water splitting method have been studied. "Resources and Energy Yearbook 1993" supervised by Agency for Natural Resources and Energy, published by the Inter-Annual Materials Survey, 1992, pp812; "Prospects and applications of electrocatalysis" edited by Hideaki Kita, published by IPC, 1990; "Technology Forecast Series No. 1" Volume 2, Energy, Chapter 11, Hydrogen Energy System "Tokio Ohta, published by Japan Business Report, 1985, pp131]. Among them, various studies have been made particularly on the method of producing hydrogen by using electrolysis of water as a promising method in which energy is easily available. However, in this electrolysis, the overvoltage at the electrodes lowers the electrolysis efficiency, which is one of the factors that hinder the efficient conversion of electric energy into chemical energy. Therefore, the electrolysis method has not yet reached the point of being practical as a method for producing hydrogen as an energy source.
【０００４】しかしながら、上記の光合成活性中心に類
似の４電子酸化触媒が開発されれば、陽電極上での酸素
発生に伴う過電圧を減じるものとなり得るため、電気分
解法が水素生産法として利用することが可能になり得
る。However, if a four-electron oxidation catalyst similar to the above-mentioned photosynthetic active center is developed, it is possible to reduce the overvoltage associated with the oxygen generation on the positive electrode, so that the electrolysis method is used as a hydrogen production method. It can be possible.
【０００５】既に発明者等は、ポルフィリン配位子を持
つマンガン単核錯体触媒を開発し、これらの触媒がオレ
フィンのエポキシ化、スルフィドのスルホキシド化など
の酸化反応に有効であることを見出している〔例えば、
Y.Naruta, F.Tani, K.Maruyama, Chemical Communicati
ons, 1990, p1378.；Y.Naruta, F.Tani, K.Maruyama,Te
trahedron, Asymmetry, 2, p533 (1991).〕。しかしな
がら、これらの触媒による酸化反応は２電子酸化反応と
考えられており、このままではこの触媒による水の４電
子酸化反応を行なうことはできない。The present inventors have already developed manganese mononuclear complex catalysts having a porphyrin ligand, and found that these catalysts are effective for oxidation reactions such as epoxidation of olefins and sulfoxide of sulfides. [For example,
Y.Naruta, F.Tani, K.Maruyama, Chemical Communicati
ons, 1990 , p1378 .; Y. Naruta, F. Tani, K. Maruyama, Te
trahedron, Asymmetry, 2 , p533 (1991).]. However, the oxidation reaction by these catalysts is considered to be a 2-electron oxidation reaction, and the 4-electron oxidation reaction of water by this catalyst cannot be carried out as it is.
【０００６】また、発明者等はマンガン＝カタラーゼの
モデルとして本発明に類似のマンガン＝ポルフィリン二
核錯体を開発しこれを用いた過酸化水素の分解反応を検
討した〔Y.Naruta, K.Maruyama, J.Am.Chem.Soc., 113,
p3595 (1991)；Y.Naruta, M,Sasayama, K.Maruyama, Ch
em.Lett., 1992, p1267.〕。これによりこの種の二核マ
ンガン＝ポルフィリン錯体が水の電気分解において触媒
機能を持つ可能性が示されてはいた。また２つのポルフ
ィリン骨格を有する配位子化合物については Collman
等も合成している〔J. P. Collman, et al., J. Am. Ch
em. Soc., 105,p2694 (1983).〕。しかし、これらの触
媒ではそのポルフィリン骨格のメソ位に水素を有するた
め、酸化反応に対して十分には安定ではなく電極修飾剤
としての利用は困難が伴うと考えられた。The present inventors have also developed a manganese porphyrin binuclear complex similar to the present invention as a model of manganese catalase, and investigated the decomposition reaction of hydrogen peroxide using this [Y. Naruta, K. Maruyama. , J. Am. Chem. Soc., 113 ,
p3595 (1991); Y. Naruta, M, Sasayama, K. Maruyama, Ch.
em. Lett., 1992 , p1267.]. This suggests that this type of binuclear manganese porphyrin complex may have a catalytic function in the electrolysis of water. See also Collman for ligand compounds with two porphyrin skeletons.
Have also been synthesized [JP Collman, et al., J. Am. Ch.
em. Soc., 105 , p2694 (1983).]. However, since these catalysts have hydrogen at the meso position of the porphyrin skeleton, they were not sufficiently stable against the oxidation reaction and were considered to be difficult to use as electrode modifiers.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、水溶液系の
電極反応において陽極において酸素発生時に生じる過電
圧を減じさしめる能力をもつ電極修飾用の新規な二核マ
ンガン＝ポルフィリン錯体を提供するものであり、その
酸化反応用の電極を提供し、さらにその電極を利用した
効率的な電気化学反応方法を提供することにある。DISCLOSURE OF THE INVENTION The present invention provides a novel binuclear manganese porphyrin complex for electrode modification which has the ability to reduce the overvoltage generated during oxygen generation at the anode in an aqueous electrode reaction. It is to provide an electrode for the oxidation reaction, and to provide an efficient electrochemical reaction method using the electrode.
【０００８】[0008]
【課題を解決するための手段】本発明は、下記一般式化
２で示される新規な二核マンガン＝ポルフィリン錯体、
及びこれを用いて修飾した電極、並びにこの電極を用い
る電気化学的反応方法からなるものである。The present invention provides a novel binuclear manganese porphyrin complex represented by the following general formula 2,
And an electrode modified with the same, and an electrochemical reaction method using the electrode.
【０００９】[0009]
【化２】 [Chemical 2]
【００１０】この化２の式中、Ａｒ及びＡｒ'は、当該
反応において酸化などの変性を受けない、例えばフェニ
ル基、トリル基、４-ｔ-ブチルフェニル基、メシチル
基、ペンタフルオロフェニル基等の置換基を有すること
もある芳香族性基一般であり、このＡｒとＡｒ'は同じ
基であっても、異なる基であっても良い。また、Ｘはマ
ンガンの対アニオンで、陰イオンであれば特に制限はな
い。In the formula (2), Ar and Ar ′ are not modified by oxidation in the reaction, for example, phenyl group, tolyl group, 4-t-butylphenyl group, mesityl group, pentafluorophenyl group, etc. It is a general aromatic group which may have a substituent of, and Ar and Ar ′ may be the same group or different groups. Further, X is a counter anion of manganese and is not particularly limited as long as it is an anion.
【００１１】上記化合物としては、Ａｒ及びＡｒ'がと
もに、ペンタフルオロフェニル基、２,４,６-トリメチ
ルフェニル基、または４-t-ブチルフェニル基をもつ二
核マンガン＝ポリフィリン、或いはＡｒが２,４,６-ト
リメチルフェニル基で、Ａｒ'がペンタフルオロフェニ
ル基または４-t-ブチルフェニル基をもつ二核マンガン
＝ポリフィリン核で、対アニオンが塩素、臭素、ヨウ素
或いは酢酸アニオン等からなる二核マンガン＝ポルフィ
リン錯体を例示することができる。As the above compound, binuclear manganese porphyrin having a pentafluorophenyl group, a 2,4,6-trimethylphenyl group or a 4-t-butylphenyl group as both Ar and Ar ', or Ar having 2 , 4,6-Trimethylphenyl group, Ar 'is a binuclear manganese = porphyrin nucleus having a pentafluorophenyl group or a 4-t-butylphenyl group, and a counter anion consisting of chlorine, bromine, iodine or acetate anion. A nuclear manganese = porphyrin complex can be illustrated.
【００１２】本発明の一般式化２で表される二核マンガ
ン＝ポルフィリン錯体は、対応するポルフィリン配位子
とマンガン塩、例えば酢酸マンガン、臭化マンガン、ヨ
ウ化マンガンより合成される。この対応するポルフィリ
ン配位子は、下記式１に示すようなスキームで合成する
ことができる。The binuclear manganese = porphyrin complex represented by the general formula 2 of the present invention is synthesized from the corresponding porphyrin ligand and manganese salt, for example, manganese acetate, manganese bromide, manganese iodide. This corresponding porphyrin ligand can be synthesized by a scheme as shown in the following formula 1.
【００１３】[0013]
【式１】 [Formula 1]
【００１４】すなわち、アルキル４-ホルミル安息香酸
を、例えば、ペンタフルオロベンズアルデヒド、２,４,
６-トリメチルフェニルアルデヒド、４-t-ブチルフェニ
ルアルデヒド等の置換基を有することもある芳香族アル
デヒドとピロールとを室温付近で、反応させ、次いで
２,３-ジクロロ-５,６-ジシアノベンゾキノンを加え
て、反応させる（Ｉ）。これで得られる１の化合物を、
LiAlH4等の還元剤で還元する（II)。還元物である２の
化合物を二酸化マンガン等の酸化剤で酸化し（III）、
３の化合物を上述したように芳香族アルデヒド及びピロ
ーツルと反応させ、次いで２,３-ジクロロ-５,６-ジシ
アノベンゾキノンと反応させ（IV）、分離精製すること
により得られる。That is, an alkyl 4-formylbenzoic acid is converted, for example, into pentafluorobenzaldehyde, 2,4,
An aromatic aldehyde which may have a substituent such as 6-trimethylphenyl aldehyde and 4-t-butylphenyl aldehyde is reacted with pyrrole at room temperature, and then 2,3-dichloro-5,6-dicyanobenzoquinone is reacted. In addition, it is reacted (I). The compound 1 thus obtained is
It is reduced with a reducing agent such as LiAlH 4 (II). The compound of 2 which is a reduced product is oxidized with an oxidizing agent such as manganese dioxide (III),
It is obtained by reacting the compound of 3 with an aromatic aldehyde and pyrozul as described above, and then with 2,3-dichloro-5,6-dicyanobenzoquinone (IV), followed by separation and purification.
【００１５】この二核マンガン＝ポルフィリン錯体は、
電極上に固定して反応を行なうことも可能であるが、２
室型の電解セルを用いてその陽極側の電解溶液中にこの
錯体を溶かし込むことによっても十分にその機能を発現
する。The binuclear manganese porphyrin complex is
It is also possible to carry out the reaction by fixing it on the electrode.
The function is sufficiently exhibited by dissolving this complex in the electrolytic solution on the anode side using a chamber-type electrolytic cell.
【００１６】本錯体により修飾される電極反応として
は、陽極側に水の酸化に伴う酸素の発生を見るものであ
れば特に制限は無い。より具体的には水の電気分解、ケ
トンの還元など陰極側において有用な物質生産を行なう
反応を例示することができる。The electrode reaction modified with the present complex is not particularly limited as long as the generation of oxygen accompanying the oxidation of water is observed on the anode side. More specifically, a reaction for producing a useful substance on the cathode side such as electrolysis of water and reduction of ketone can be exemplified.
【００１７】本発明における電解溶液としては、十分な
電解質と水分とさらに本発明の錯体を溶かすことが可能
であれば、特に制限は無い。具体的には水、アセトニト
リル、スルホランの混合溶媒等を例示することができ
る。また電解質は反応や溶媒に応じて選択すればよい。The electrolytic solution in the present invention is not particularly limited as long as it can dissolve sufficient electrolyte, water and the complex of the present invention. Specifically, a mixed solvent of water, acetonitrile and sulfolane can be exemplified. The electrolyte may be selected depending on the reaction and solvent.
【００１８】本発明の錯体は２つのポルフィリン骨格を
有するものであるが、このポルフィリン骨格を配位子と
するマンガンイオンは通常の３価の状態の他に高酸化状
態として４価あるいは５価を取り得るようになる。これ
により１つの金属中心は２電子酸化触媒と成ることが可
能になる。さらに加えて、２つのマンガン金属中心が本
発明のごとく適当な距離と配向を持つことによりこの２
つの金属中心が共同して４電子酸化を行なうことが可能
になり、それにより本発明の二核マンガン錯体は水の酸
化を触媒することが可能になるという格別の効果を持つ
に至っている。実際に、本発明のような構造を持たない
単核のマンガン＝ポルフィリン錯体においては陽極にお
ける酸素の発生過程を触媒することにより陽極の過電圧
を減じる能力は認められなかった。The complex of the present invention has two porphyrin skeletons. The manganese ion having the porphyrin skeleton as a ligand has a trivalent state or a tetravalent or pentavalent state as a highly oxidized state. Will be available. This allows one metal center to serve as a two-electron oxidation catalyst. In addition, the two manganese metal centers have the proper distance and orientation as in the present invention.
The two metal centers can jointly carry out four-electron oxidation, whereby the binuclear manganese complex of the present invention has a special effect that it can catalyze the oxidation of water. In fact, in the mononuclear manganese-porphyrin complex having no structure as in the present invention, the ability to reduce the overvoltage of the anode by catalyzing the oxygen generation process at the anode was not recognized.
【００１９】また本発明のポルフィリン触媒配位子の骨
格上のメソ位の水素はすべて芳香族性基によって置換さ
れているが、これにより、通常は酸化反応により分解さ
れやすいポルフィリン骨格が酸化的な条件下においても
安定に存在し、触媒活性を保つことができる様になる。
次に本発明を実施例を示して具体的に説明する。Further, all of the meso hydrogens on the skeleton of the porphyrin catalyst ligand of the present invention are replaced by aromatic groups, which usually causes the porphyrin skeleton, which is easily decomposed by an oxidation reaction, to be oxidative. It exists stably under the conditions and can keep the catalytic activity.
Next, the present invention will be specifically described with reference to examples.
【００２０】[0020]
（合成例）メチル４-ホルミル安息香酸１.６０g(９.７
６mmol)、ペンタフルオロベンズアルデヒド１０.２１g
(５２.８mmol)、ピロール４.２０g(６２.６mmol)をクロ
ロホルム８００mlに溶解した後、この溶液に窒素ガスを
吹き込んだ。十分窒素置換をした後、三フッ化ホウ素エ
ーテル錯塩４.１８mlを加え、暗所にて窒素雰囲気を保
ち、２４時間、室温で撹拌した。(Synthesis example) Methyl 4-formylbenzoic acid 1.60 g (9.7
6mmol), pentafluorobenzaldehyde 10.21g
(52.8 mmol) and 4.20 g (62.6 mmol) of pyrrole were dissolved in 800 ml of chloroform, and then nitrogen gas was blown into this solution. After sufficiently substituting with nitrogen, 4.18 ml of boron trifluoride ether complex salt was added, and the mixture was stirred at room temperature for 24 hours while maintaining a nitrogen atmosphere in the dark.
【００２１】この反応混合液に、２,３-ジクロロ-５,６
-ジシアノベンゾキノン３gのベンゼン溶液を加え、０.
５時間、暗所にて撹拌した後、この反応溶液を炭酸水素
ナトリウム水溶液で数回洗った。有機層を無水硫酸ナト
リウムで乾燥した後、溶媒を減圧下に留去した。残渣を
シリカゲルカラムクロマトフラフィー(溶融液：ベンゼ
ン-ヘキサン)を用いて分離し、下記物性を有する化合物
を得た。この化合物は、下記物性等から前記式１のスキ
ーム中に示した化合物１でＡｒがペンタフルオロフェニ
ル基を持つものであることが同定された(収率２５％)。1 Ｈ-ＮＭＲ(CDCl3,δppm)：２.７７(br,2H,NH)、２.８
２(s,3H,Me)、７.９０(d,2H)、８.２５(d,1H)、８.３５
(d,1H)、８.８１(s,4H)、８.９４(s,4H) ＦＡＢ ＭＳ(m/z)：９４３(M＋H+)To this reaction mixture was added 2,3-dichloro-5,6.
-Add a solution of 3 g of dicyanobenzoquinone in benzene and add
After stirring for 5 hours in the dark, the reaction solution was washed several times with an aqueous sodium hydrogen carbonate solution. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The residue was separated using silica gel column chromatography (melt: benzene-hexane) to obtain a compound having the following physical properties. It was identified from the following physical properties that this compound is compound 1 shown in the scheme of Formula 1 above, in which Ar has a pentafluorophenyl group (yield 25%). 1 H-NMR (CDCl 3 , δppm): 2.77 (br, 2H, NH), 2.8
2 (s, 3H, Me), 7.90 (d, 2H), 8.25 (d, 1H), 8.35
(d, 1H), 8.81 (s, 4H), 8.94 (s, 4H) FAB MS (m / z): 943 (M + H + )
【００２２】次に、上記で得られた化合物１を過剰量の
水素化アルミニウムリチウムとエーテル中で反応させ、
後処理をした後、有機層を乾燥、乾固し、下記物性を有
する化合物を定量的に得た。この化合物は、下記物性等
から前記式１のスキーム中に示した化合物２でＡｒがペ
ンタフルオロフェニル基を持つものであることが同定さ
れた。1 Ｈ-ＮＭＲ(CDCl3,δppm):２.７０(br,2H)、５.２８(b
r,2H)、７.２０(m,2H)、７.６６(d,2H)、８.９１(d,4
H)、８.９８(d,4H) ＦＡＢ ＭＳ(m/z)：９１５(M＋H+)Then, the compound 1 obtained above is reacted with an excess amount of lithium aluminum hydride in ether,
After post-treatment, the organic layer was dried and dried to quantitatively obtain a compound having the following physical properties. It was identified from the following physical properties that this compound was compound 2 shown in the scheme of Formula 1 above, in which Ar had a pentafluorophenyl group. 1 H-NMR (CDCl 3 , δppm): 2.70 (br, 2H), 5.28 (b
r, 2H), 7.20 (m, 2H), 7.66 (d, 2H), 8.91 (d, 4)
H), 8.98 (d, 4H) FAB MS (m / z): 915 (M + H + )
【００２３】活性二酸化マンガン１０gをクロロホルム
に懸濁し、上記で得た化合物２を加えて、暗所で１２時
間撹拌した。沈殿を濾過した後、濾液を減圧下で濃縮し
た。残渣のクロロホルム溶液をシリカゲル層を通して濾
過し、下記物性を有する化合物を定量的に得た。この化
合物は、下記物性等から前記式１のスキーム中に示した
化合物３でＡｒがペンタフルオロフェニル基を持つもの
であることが同定された(収率９５％)。1 Ｈ-ＮＭＲ(CDCl3,δppm)：２.７８(s,2H)、７.９５(d
t,1H,J=1.7,7.2Hz)、７.９８(t,1H,J=7.2Hz)、８.０２
(d,1H,J=7.2Hz)、８.４４(dd,1H,J=1.7,7.2Hz)、８.７
６(d,2H,J=4.7Hz)、８.８２(d,2H,J=4.7Hz)、８.９０
(s,4H)９.４９(s,1H) ＦＡＢ ＭＳ(m/z)：９１３(M＋H+)10 g of active manganese dioxide was suspended in chloroform, the compound 2 obtained above was added, and the mixture was stirred for 12 hours in the dark. After filtering the precipitate, the filtrate was concentrated under reduced pressure. A chloroform solution of the residue was filtered through a silica gel layer to quantitatively obtain a compound having the following physical properties. It was identified from the above-mentioned physical properties that this compound is the compound 3 shown in the scheme of the above formula 1 in which Ar has a pentafluorophenyl group (yield 95%). 1 H-NMR (CDCl 3 , δppm): 2.78 (s, 2H), 7.95 (d
t, 1H, J = 1.7,7.2Hz), 7.98 (t, 1H, J = 7.2Hz), 8.02
(d, 1H, J = 7.2Hz), 8.44 (dd, 1H, J = 1.7,7.2Hz), 8.7
6 (d, 2H, J = 4.7Hz), 8.82 (d, 2H, J = 4.7Hz), 8.90
(s, 4H) 9.49 (s, 1H) FAB MS (m / z): 913 (M + H + )
【００２４】上記で得られた化合物３を４６８mg(０.５
１３mmol)、ペンタフルオロベンズアルデヒドを１.０８
g(５.５０mmol)及びピロールを４０３mg(６.０２mmo
l)、それぞれクロロホルム２８０mlに溶かし、窒素置換
を行った後、三フッ化ホウ素エ−テル錯塩５６０μlを
加える。暗所、窒素雰囲気下、室温で２４時間撹拌した
後、２,３-ジクロロ-５,６-ジシアノベンゾキノン２gを
加え、さらに０.５時間撹拌した。反応溶液は炭酸水素
ナトリウム水溶液で繰り返し洗浄した後、乾燥、エバポ
レートした。残渣をカラムクロマトグラフィーにて分離
精製し、下記物性を有する化合物が得られ、この化合物
は、下記物性等から前記式１のスキーム中に示した化合
物４でＡｒ及びＡｒ'がペンタフルオロフェニル基を持
つものであることが同定された(収率１５％)。1 Ｈ-ＮＭＲ(CDCl3,δppm)：４.０４(br,s)、７.３９(b
r,1H)、８.４３(s,12H)、 ８.６４(br,1H)、８.９
０(br,2H)、９.３８(s,4H) ＦＡＢ ＭＳ(m/z)：１６９１(M＋H+)468 mg (0.5) of the compound 3 obtained above
13 mmol) and 1.08 of pentafluorobenzaldehyde
g (5.50 mmol) and 403 mg (6.02 mmo) of pyrrole
l), each of which was dissolved in 280 ml of chloroform and nitrogen substitution was performed, and then 560 μl of boron trifluoride ether complex salt was added. After stirring at room temperature for 24 hours in a dark place under a nitrogen atmosphere, 2 g of 2,3-dichloro-5,6-dicyanobenzoquinone was added, and the mixture was further stirred for 0.5 hour. The reaction solution was repeatedly washed with an aqueous sodium hydrogen carbonate solution, dried, and evaporated. The residue is separated and purified by column chromatography to obtain a compound having the following physical properties. This compound is compound 4 shown in the scheme of Formula 1 above in which Ar and Ar ′ are pentafluorophenyl groups due to the following physical properties and the like. It was identified as having (yield 15%). 1 H-NMR (CDCl 3 , δppm): 4.04 (br, s), 7.39 (b
r, 1H), 8.43 (s, 12H), 8.64 (br, 1H), 8.9
0 (br, 2H), 9.38 (s, 4H) FAB MS (m / z): 1691 (M + H + )
【００２５】上記で得た化合物４と過剰量の酢酸マンガ
ン(II)を酢酸に溶解し、２時間還流した。可視紫外スペ
クトルにより、フリーベースのポルフィリンが残存して
いないことを確認した後、減圧下で溶媒を留去した。残
渣に希塩酸水溶液と塩化メチレンを加え、固体を溶解
し、水層を分離した後、塩化メチレン層を希塩酸水溶液
で洗った。この溶液を濃縮乾固した後、シリカゲルカラ
ムクロマトグラフィー(溶出液は塩化メチレン-メタノー
ル混合液)で精製した。The compound 4 obtained above and an excess amount of manganese (II) acetate were dissolved in acetic acid and refluxed for 2 hours. After confirming by the visible ultraviolet spectrum that the free base porphyrin did not remain, the solvent was distilled off under reduced pressure. Dilute hydrochloric acid aqueous solution and methylene chloride were added to the residue to dissolve the solid, the aqueous layer was separated, and then the methylene chloride layer was washed with dilute hydrochloric acid aqueous solution. The solution was concentrated to dryness and then purified by silica gel column chromatography (eluent: methylene chloride-methanol mixture).
【００２６】目的生成物の留分を集め、これを順次希塩
酸水溶液、飽和食塩水と共に振とう後、乾燥食塩を集め
たカラムを通して乾燥、乾固した。この生成物を塩化メ
チレン-ヘキザンに再結晶し、純品を得た(収率９２
％)。下記物性によりマンガンが配位していることが確
認され、本発明の二核マンガン＝ポルフィリン錯体が得
られた。 ＦＡＢ ＭＳ(m/z)：１７９６(M-2Cl-) ＵＶ-vis(CH2Cl2,λnm)：３６４、４５３、５７０ 上記と同様の操作により、前述の一般式化２のＡｒ及び
Ａｒ'がともに２,４,６-トリメチルフェニルで、Ｘが塩
素からなる化合物、Ａｒ及びＡｒ'がともに４-t-ブチル
フェニルで、Ｘが塩素からなる化合物、Ａｒが２,４,６
-トリメチルフェニル、Ａｒ'がペンタフルオロフェニル
で、Ｘが塩素からなる化合物、Ａｒが２,４,６-トリメ
チルフェニル、Ａｒ'が４-t-ブチルフェニルで、Ｘが塩
素からなる化合物を合成した。Fractions of the desired product were collected, shaken successively with a dilute hydrochloric acid aqueous solution and saturated saline, dried through a column containing dried salt, and dried. This product was recrystallized from methylene chloride-hexan to obtain a pure product (yield 92
%). It was confirmed by the following physical properties that manganese was coordinated, and the binuclear manganese = porphyrin complex of the present invention was obtained. FAB MS (m / z): 1796 (M-2Cl − ) UV-vis (CH 2 Cl 2 , λnm): 364, 453, 570 By the same operation as above, Ar and Ar ′ in the general formula 2 above. Are both 2,4,6-trimethylphenyl and X is chlorine, Ar and Ar 'are both 4-t-butylphenyl and X is chlorine, and Ar is 2,4,6.
-A compound having trimethylphenyl, Ar 'being pentafluorophenyl and X being chlorine, a compound having Ar being 2,4,6-trimethylphenyl, Ar' being 4-t-butylphenyl and X being chlorine was synthesized. .
【００２７】（電気化学反応）セル外側に恒温水流通用
のジャケットを持ち、各室３mlの容量を持ち、さらに２
室間がグラスフィルターで隔離された２室型電解セルの
それぞれの室に、電解溶液として０.１Mの過塩素酸テト
ラブチルアンモニウム、０.００５Mの水酸化テトラブチ
ルアンモニウム、２％の水、１０％のスルホランを含む
アセトニトリル溶液をそれぞれ２.５mlづつ入れる。陽
極側には上記方法で合成した表１に示したＡｒ及びＡ
ｒ'を持つ一般式化２の二核マンガン＝ポルフィリン２.
５μmolを加え、０.１Mの過塩素酸銀水溶液中に銀線を
入れた参照電極を挿入した。さらに各室に白金網電極を
挿入し、それぞれの室の電解溶液中の溶存酸素をアルゴ
ンガスを用いて追い出した。恒温水により電解溶液の温
度を１０℃に保ち、各電極をポテンシオスタットに接続
し、参照電極に対して＋１.４〜＋２.０Ｖの範囲で電解
した。陽極に流れた電気量はクーロメーターを用いて計
測した。(Electrochemical reaction) A jacket for circulating constant temperature water is provided outside the cell, and each chamber has a capacity of 3 ml.
0.1M tetrabutylammonium perchlorate, 0.005M tetrabutylammonium hydroxide, 2% water, 10% as an electrolytic solution were placed in each chamber of the two-chamber electrolysis cell in which the chambers were separated by a glass filter. Add 2.5 ml each of acetonitrile solutions containing% sulfolane. Ar and A shown in Table 1 synthesized by the above method on the anode side.
A binuclear manganese porphyrin of general formula 2 with r'2.
5 μmol was added, and a reference electrode containing a silver wire was inserted into a 0.1 M silver perchlorate aqueous solution. Furthermore, a platinum mesh electrode was inserted into each chamber, and dissolved oxygen in the electrolytic solution in each chamber was expelled using argon gas. The temperature of the electrolytic solution was kept at 10 ° C. with constant temperature water, each electrode was connected to a potentiostat, and electrolysis was performed in the range of +1.4 to +2.0 V with respect to the reference electrode. The amount of electricity flowing to the anode was measured using a coulometer.
【００２８】この反応において陽極側に発生した酸素を
クラ−ク型酸素電極を用いて定量し、酸素発生速度及び
電流効率を算出し、これを表１に示した。Oxygen generated on the anode side in this reaction was quantified using a Clark-type oxygen electrode, and the oxygen generation rate and current efficiency were calculated, which are shown in Table 1.
【００２９】[0029]
【表１】 [Table 1]
【００３０】これらの二核マンガン＝ポルフィリン錯体
を加えなかった場合、あるいは単核のマンガン＝ポルフ
ィリン触媒を用いた場合では、この陽極電位においての
酸素の発生は認められなかった。When these binuclear manganese porphyrin complexes were not added or when a mononuclear manganese porphyrin catalyst was used, oxygen was not generated at this anode potential.
【００３１】また、この反応において生成した気体が水
酸素原子由来の酸素であることは、Ｈ2Ｏ18を５０％含
む水を反応に供したところ、生成した酸素の質量分析の
結果、その２５％が分子量３６であり、５０％が分子量
３４であり、残りの２５％が３２であることから確認さ
れた。The fact that the gas generated in this reaction is oxygen derived from water oxygen atoms means that when water containing 50% of H 2 O 18 was subjected to the reaction, the result of mass spectrometry of the oxygen generated was 25 % Was 36, 50% was 34 and the remaining 25% was 32.
【００３２】[0032]
【発明の効果】本発明の二核マンガン＝ポルフィリン錯
体は、電極の修飾剤として用いることにより、有望なエ
ネルギー源と考えられている水素を水の電気分解によっ
て効率的に生産し、あるいはより効率的な有用化学物質
の電気化学的生産反応系等の酸素の発生を伴う効率のよ
い電気化学的な反応系の構築が可能になる。INDUSTRIAL APPLICABILITY By using the binuclear manganese porphyrin complex of the present invention as a modifier for electrodes, hydrogen, which is considered as a promising energy source, can be efficiently produced by electrolysis of water, or more efficiently. It is possible to construct an efficient electrochemical reaction system with generation of oxygen such as a electrochemical production system of a particularly useful chemical substance.
Claims (3)
性基を表わし、同じでも異なっていても良い。式中Ｘは
マンガンの対アニオンを表す）で示される新規な二核マ
ンガン＝ポルフィリン錯体。1. The following general formula 1 (Wherein Ar and Ar ′ represent an aromatic group which may have a substituent and may be the same or different; in the formula, X represents a counter anion of manganese); Porphyrin complex.
ィリン錯体により修飾された電極。2. An electrode modified with the binuclear manganese = porphyrin complex according to claim 1.
ィリン錯体により修飾された電極を用いる電気化学的反
応方法。3. An electrochemical reaction method using an electrode modified with the binuclear manganese = porphyrin complex according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP92253645A JPH0673060A (en) | 1992-08-31 | 1992-08-31 | New binuclear manganese=porphyrin complex and electrode modified therwith and method for electrochemical reaction using the electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP92253645A JPH0673060A (en) | 1992-08-31 | 1992-08-31 | New binuclear manganese=porphyrin complex and electrode modified therwith and method for electrochemical reaction using the electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0673060A true JPH0673060A (en) | 1994-03-15 |
Family
ID=17254210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP92253645A Pending JPH0673060A (en) | 1992-08-31 | 1992-08-31 | New binuclear manganese=porphyrin complex and electrode modified therwith and method for electrochemical reaction using the electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0673060A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6939630B2 (en) | 2001-08-29 | 2005-09-06 | Matsushita Electric Industrial Co., Ltd. | Composite electrode for reducing oxygen |
-
1992
- 1992-08-31 JP JP92253645A patent/JPH0673060A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6939630B2 (en) | 2001-08-29 | 2005-09-06 | Matsushita Electric Industrial Co., Ltd. | Composite electrode for reducing oxygen |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fox et al. | Photoactivation of metal oxide surfaces: photocatalyzed oxidation of alcohols by heteropolytungstates | |
| Jin et al. | Synthesis, electrochemical and spectroelectrochemical studies of metal-free 2, 9, 16, 23-tetraferrocenylphthalocyanine | |
| Collin et al. | Electrocatalytic properties of (tetraazacyclotetradecane) nickel (2+) and Ni2 (biscyclam) 4+ with respect to carbon dioxide and water reduction | |
| Manbeck et al. | Photoinitiated electron collection in polyazine chromophores coupled to water reduction catalysts for solar H2 production | |
| Roy et al. | Biomimetic model for [FeFe]-hydrogenase: asymmetrically disubstituted diiron complex with a redox-active 2, 2′-bipyridyl ligand | |
| US8524903B2 (en) | Ruthenium or osmium complexes and their uses as catalysts for water oxidation | |
| Wada et al. | Catalytic Four‐Electron Oxidation of Water by Intramolecular Coupling of the Oxo Ligands of a Bis (ruthenium–bipyridine) Complex | |
| Niu et al. | Halogen substituted A2B type Co (III) triarylcorroles: Synthesis, electronic structure and two step modulation of electrocatalyzed hydrogen evolution reactions | |
| Zhong et al. | A comparative study of electrocatalytic hydrogen evolution by iron complexes of corrole and porphyrin from acetic acid and water | |
| Zheng et al. | An electrochemical and spectroelectrochemical (IR) investigation of the reduction of RCo (II) TPP (R= benzyl or butyl; TPP= tetraphenylporphyrin): mechanistic implications in the CoTPP catalyzed electrocarboxylation of alkyl halides | |
| FR2953519A1 (en) | NOVEL CHEMICAL COMPOUNDS SUITABLE FOR COMPLEXING AT LEAST ONE METAL ELEMENT AND COORDINATION COMPLEX THEREFROM | |
| Makhado et al. | Chemical and electrochemical water oxidation mediated by bis (pyrazol-1-ylmethyl) pyridine-ligated Cu (i) complexes | |
| Chandra et al. | Remarkable enhancement of catalytic activity of Cu‐complexes in the electrochemical hydrogen evolution reaction by using triply fused porphyrin | |
| Roy et al. | Synthesis and Electrocatalytic Activity of [FeFe]‐Hydrogenase Model Complexes with Non‐Innocent Chelating Nitrogen‐Donor Ligands | |
| Xue et al. | Function of 7, 7, 8, 8-tetracyanoquinodimethane (TCNQ) on electrocatalytic hydrogen generation catalyzed by N, N′-benzene bis (salicylideniminato) nickel (II) | |
| Yoshimura et al. | A systematic study on the double-layered photosensitizing dye structure on the surface of Pt-cocatalyst-loaded TiO2 nanoparticles | |
| Hernández-Valdés et al. | [Re (η 6-arene) 2]+ as a highly stable ferrocene-like scaffold for ligands and complexes | |
| Butler et al. | Ferrocenyl anthracenes: Synthesis and molecular structure | |
| Kärkäs et al. | Light‐Induced Water Oxidation by a Ru complex Containing a Bio‐Inspired Ligand | |
| JPH0673060A (en) | New binuclear manganese=porphyrin complex and electrode modified therwith and method for electrochemical reaction using the electrode | |
| JP3432692B2 (en) | Binuclear iron complex catalyst | |
| Lai et al. | Electrochemistry of oxo-bridged ruthenium dimers with 4, 4′-dichloro-and 5, 5′-dichloro-2, 2′-bipyridine and their catalytic properties towards water oxidation | |
| El Murr et al. | Electrochemistry of half-sandwich and trinuclear sandwich complexes containing phosphonate ligands | |
| Tang et al. | Electrochemical and photochemical hydrogen generation by a water soluble cobalt (II) complex of 2, 2-bipyridine | |
| Shimidzu et al. | Photoredox and electrochemical reactions of water-soluble gold porphyrins |