JP3117737B2 - Purification method of organometallic complex - Google Patents
Purification method of organometallic complexInfo
- Publication number
- JP3117737B2 JP3117737B2 JP03059640A JP5964091A JP3117737B2 JP 3117737 B2 JP3117737 B2 JP 3117737B2 JP 03059640 A JP03059640 A JP 03059640A JP 5964091 A JP5964091 A JP 5964091A JP 3117737 B2 JP3117737 B2 JP 3117737B2
- Authority
- JP
- Japan
- Prior art keywords
- organometallic complex
- group
- purifying
- extraction solvent
- metal
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/77—Preparation of chelates of aldehydes or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、薄膜、超電導材料、透
光性セラミック材料、または燃料電池材料などとして用
いられる有機金属錯体の精製法に関する。The present invention relates to a method for purifying an organometallic complex used as a thin film, a superconducting material, a translucent ceramic material, a fuel cell material, or the like.
【０００２】[0002]
【従来の技術】従来、単結晶薄膜や多結晶薄膜の形成方
法として、ドライプロセスとウエットプロセスといった
２種類の方法が用いられてきたが、ウエットプロセスと
比べてドライプロセスによって形成された薄膜のほうが
品質面で優れるため、ドライプロセスが多用さているの
が現状である。2. Description of the Related Art Conventionally, two types of methods, a dry process and a wet process, have been used as a method of forming a single crystal thin film or a polycrystalline thin film. However, a thin film formed by a dry process is better than a wet process. At present, dry processes are frequently used because of their excellent quality.
【０００３】ドライプロセスには、真空蒸着法、イオン
プレーティング法およびスパッタリング法等の物理的成
膜法と、化学的気相蒸着法（ＣＶＤ法）等の化学的成膜
法とがある。中でもＣＶＤ法は、成膜速度の制御が容易
である上、成膜を高真空下で行う必要がなく、しかも高
速成膜が可能であることなどから量産向きであるため広
く用いられている。このようなＣＶＤ法において、有機
金属錯体の蒸気を分解させて金属薄膜を形成する場合に
は、熱ＣＶＤ法、光ＣＶＤ法またはプラズマＣＶＤ法が
採用される。また、これらの方法では、有機部分（配位
子）がアセチルアセトン、ジピバロイルメタンまたはジ
イソブチリルメタン等からなる有機金属錯体が一般的に
使用されている。The dry process includes a physical film forming method such as a vacuum evaporation method, an ion plating method and a sputtering method, and a chemical film forming method such as a chemical vapor deposition method (CVD method). Above all, the CVD method is widely used because it is easy to control the film formation rate, does not need to perform film formation under a high vacuum, and is suitable for mass production because high-speed film formation is possible. In such a CVD method, when a metal thin film is formed by decomposing a vapor of an organometallic complex, a thermal CVD method, a photo CVD method, or a plasma CVD method is employed. In these methods, an organic metal complex whose organic portion (ligand) is composed of acetylacetone, dipivaloylmethane, diisobutyrylmethane, or the like is generally used.
【０００４】しかしながら、上記のような方法によって
有機金属錯体から金属薄膜を形成した場合、有機金属錯
体の純度不足から、得られる成膜材料中に金属不純物が
取り込まれ、薄膜の電気的性質や化学的性質を低下させ
るという問題点があった。そのため、従来の技術では金
属薄膜の形成に使用される有機金属錯体を、直接昇華精
製または再結晶精製を繰り返し行うことにより、その純
度の向上を計っていたが、これらの方法は手間がかかる
上、不純物の除去が完全でないため対応策が求められて
いた。However, when a metal thin film is formed from an organometallic complex by the above-described method, metal impurities are taken into the obtained film-forming material due to insufficient purity of the organometallic complex, and the electrical properties and chemical properties of the thin film are reduced. There is a problem that the physical properties are deteriorated. Therefore, in the prior art, the purity of an organometallic complex used for forming a metal thin film was improved by repeatedly performing direct sublimation purification or recrystallization purification. However, these methods are troublesome. However, since the removal of impurities is not complete, a countermeasure has been required.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上述従来の
技術の問題点を解決し、簡便に有機金属錯体の純度を十
分に向上させることができる有機金属錯体の精製法の提
供を目的としている。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a method for purifying an organometallic complex which can easily improve the purity of the organometallic complex easily. I have.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、上記課題
を解決するため鋭意研究したところ、原料の有機金属錯
体の粗結晶を芳香族炭化水素類または脂肪族炭化水素類
に属する特定の抽出溶剤で抽出した後、再結晶精製する
ことにより有機金属錯体の高純度化が計れることを見い
出し、本発明を達成することができた。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and found that crude crystals of the organometallic complex as a raw material are specified as aromatic hydrocarbons or aliphatic hydrocarbons. After extracting with an extraction solvent and recrystallizing and refining, it has been found that the organometallic complex can be highly purified, thereby achieving the present invention.
【０００７】すなわち、本発明は、化２で示される１，
３−ジケトン系有機化合物を配位子とする有機金属錯体
の精製法であって、上記有機金属錯体の粗結晶を芳香族
炭化水素類または脂肪族炭化水素類に属する抽出溶剤で
抽出し、その抽出液から抽出溶剤を除去して得た結晶物
を再結晶精製することを特徴とする有機金属錯体の精製
法を提供するものである。That is, the present invention relates to
A method for purifying an organometallic complex having a 3-diketone organic compound as a ligand, wherein crude crystals of the organometallic complex are extracted with an extraction solvent belonging to aromatic hydrocarbons or aliphatic hydrocarbons, An object of the present invention is to provide a method for purifying an organometallic complex, comprising recrystallizing and purifying a crystal obtained by removing an extraction solvent from an extract.
【０００８】[0008]
【化２】 （ただし、式中Ｒ1 およびＲ2 はそれぞれ独立にメチル
基、イソプロピル基およびｔ−ブチル基からなる群より
選ばれる１種の基を表す。）Embedded image (Wherein, R 1 and R 2 each independently represent one group selected from the group consisting of a methyl group, an isopropyl group, and a t-butyl group.)
【０００９】また、上記有機金属錯体における中心金属
元素は、 IIIＡ金属またはIVＡ族金属に属するものであ
るとより好都合である。It is more convenient that the central metal element in the organometallic complex belongs to a IIIA metal or a group IVA metal.
【００１０】さらに、上記抽出溶剤としては、芳香族炭
化水素類であればベンゼン、トルエンまたはキシレン、
脂肪族炭化水素類であればペンタン、ヘキサン、ヘプタ
ン、２−メチルヘキサンまたはオクタンなどといったよ
うなアルキル基の炭素数が５〜８である化合物を用いる
と特に好ましい。Further, as the above-mentioned extraction solvent, benzene, toluene or xylene, if it is an aromatic hydrocarbon,
As the aliphatic hydrocarbon, it is particularly preferable to use a compound having an alkyl group having 5 to 8 carbon atoms, such as pentane, hexane, heptane, 2-methylhexane or octane.
【００１１】本発明を詳細に説明すると次の通りであ
る。まず、化３で示される有機化合物のＮａ塩またはＫ
塩と、金属無機酸塩（塩化物、硝酸塩またはオキシ硝酸
塩）との水−アルコール溶液からの合成によって有機金
属錯体溶液を作成する。次に、作成した有機金属錯体溶
液からアルコールを除去した後、それを濾過して有機金
属錯体の粗結晶を得る。The present invention will be described in detail as follows. First, Na salt or K of an organic compound represented by Chemical Formula 3
An organometallic complex solution is prepared by synthesis of a salt and a metal inorganic acid salt (chloride, nitrate or oxynitrate) from a water-alcohol solution. Next, after removing the alcohol from the prepared organometallic complex solution, it is filtered to obtain crude crystals of the organometallic complex.
【００１２】[0012]
【化３】 （ただし、式中Ｒ1 およびＲ2 はそれぞれ独立にメチル
基、イソプロピル基およびｔ−ブチル基からなる群より
選ばれる１種の基を表す。）Embedded image (Wherein, R 1 and R 2 each independently represent one group selected from the group consisting of a methyl group, an isopropyl group, and a t-butyl group.)
【００１３】上記のようにして得られた有機金属錯体の
粗結晶を、芳香族炭化水素類または脂肪族炭化水素類に
属する抽出溶剤を用いて抽出することにより、該有機金
属錯体に副生する無機Ｎａ塩や無機Ｋ塩などの無機化合
物を除去する。上記抽出工程後、得られた抽出液から抽
出溶剤を除去して有機金属錯体の結晶物を得、その結晶
物をアルコールまたはジメチルホルムアミドなどで加湿
溶解させる。加湿溶解後、その溶液を室温に放置して再
結晶物を得、その再結晶物を減圧加熱乾燥して高純度の
有機金属錯体を得る。The crude crystals of the organometallic complex obtained as described above are extracted as a by-product into the organometallic complex by extracting the crude crystals with an extraction solvent belonging to aromatic hydrocarbons or aliphatic hydrocarbons. Inorganic compounds such as inorganic Na salt and inorganic K salt are removed. After the extraction step, the extraction solvent is removed from the obtained extract to obtain a crystal of the organometallic complex, and the crystal is humidified and dissolved with an alcohol or dimethylformamide. After humidification and dissolution, the solution is left at room temperature to obtain a recrystallized product, and the recrystallized product is dried by heating under reduced pressure to obtain a highly pure organometallic complex.
【００１４】なお、本発明における再結晶工程は、２回
繰り返せば十分である。Incidentally, it is sufficient to repeat the recrystallization step twice in the present invention.
【００１５】[0015]
【作用】本発明は、芳香族炭化水素類または脂肪族炭化
水素類の抽出溶剤による抽出工程を再結晶精製の前処理
として設けたことに最大の特徴がある。このように抽出
工程を設けることにより、抽出工程と繰り返し回数の少
ない再結晶工程という簡便な操作で有機金属錯体の高純
度化が計れるようになる。The present invention is most characterized in that an extraction step of an aromatic hydrocarbon or an aliphatic hydrocarbon with an extraction solvent is provided as a pretreatment for recrystallization purification. By providing the extraction step as described above, the purification of the organometallic complex can be achieved by a simple operation of the extraction step and the recrystallization step with a small number of repetitions.
【００１６】また、本発明では配位子がアセチルアセト
ン、ジピバロイルメタンまたはジイソブチリルメタンで
ある有機金属錯体を用いると好都合である。In the present invention, it is advantageous to use an organometallic complex whose ligand is acetylacetone, dipivaloylmethane or diisobutyrylmethane.
【００１７】本発明の有機金属錯体の精製法によると、
金属不純物としてのＦｅ、Ｃｏ、Ｎｉ、ＮａおよびＫの
含有量が、いずれも検出限界の１ppm 以下にまで低下す
る。金属薄膜を形成する際に原料として用いられる有機
金属錯体の含有する金属不純物量が１ppm 以下であれ
ば、形成される金属薄膜の電気的性質および化学的性質
が変化することはない。According to the method for purifying an organometallic complex of the present invention,
The contents of Fe, Co, Ni, Na and K as metal impurities are all reduced to the detection limit of 1 ppm or less. If the amount of metal impurities contained in the organometallic complex used as a raw material when forming the metal thin film is 1 ppm or less, the electrical properties and chemical properties of the formed metal thin film do not change.
【００１８】以下、実施例により本発明をさらに詳細に
説明する。しかし本発明の範囲は、以下の実施例により
制限されるものではない。Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.
【００１９】[0019]
【実施例１】まず、Ｙ（ＮＯ3 ）3 とＮａＤＰＭ（ジピ
バロイルメタナトナトリウム）との合成により有機金属
錯体の粗結晶（Ｙ（ＤＰＭ）3 ・ＮａＮＯ3 ）50ｇを作
製し、得られた粗結晶50ｇに対してｎ−ヘキサンを抽出
溶剤として 500ml加えて室温下で撹拌溶解させ、Ｙ（Ｄ
ＰＭ）3 を抽出した。次いで得られた抽出液を加圧濾過
（３ＫＧ）後、減圧加温（１mmHg、40℃、１Hr）して抽
出液中のｎ−ヘキサンを除去し、Ｙ（ＤＰＭ）3 （ジピ
バロイルメタナトイットリウム）の結晶物35ｇを得た。Example 1 First, 50 g of a crude crystal of an organometallic complex (Y (DPM) 3 .NaNO 3 ) was prepared by synthesizing Y (NO 3 ) 3 and NaDPM (sodium dipivaloylmethanato). To 50 g of the crude crystals thus obtained, 500 ml of n-hexane was added as an extraction solvent, and the mixture was stirred and dissolved at room temperature.
PM) 3 . Then, the obtained extract was subjected to pressure filtration (3KG), and then heated under reduced pressure (1 mmHg, 40 ° C, 1Hr) to remove n-hexane in the extract, and Y (DPM) 3 (dipivaloylmethanato) was removed. 35 g of crystals of (yttrium) were obtained.
【００２０】次に、得られた35ｇの結晶物は、ジメチル
ホルムアミドで加温溶解させた後、これを室温で放置す
るという操作を２回行い再結晶物を得た。その後、該再
結晶物を減圧加熱乾燥することにより、高純度の有機金
属錯体（Ｙ（ＤＰＭ）3 ）28ｇを得た。Next, 35 g of the obtained crystal was heated and dissolved in dimethylformamide, and then left at room temperature twice to obtain a recrystallized product. Thereafter, the recrystallized product was dried by heating under reduced pressure to obtain 28 g of a high-purity organometallic complex (Y (DPM) 3 ).
【００２１】このようにして得られたＹ（ＤＰＭ）3 に
おける不純物含有量の測定を行った。測定は、得られた
Ｙ（ＤＰＭ）3 を王水に溶解させて調整したものを試料
とし、ＩＣＰにより金属不純物の測定を行った。その結
果、金属不純物としてのＦｅ、Ｃｏ、Ｎｉ、Ｎａまたは
Ｋは、いずれも１ppm 以下であった。The impurity content of Y (DPM) 3 thus obtained was measured. The measurement was performed by dissolving the obtained Y (DPM) 3 in aqua regia and using the sample as a sample to measure metal impurities by ICP. As a result, Fe, Co, Ni, Na or K as metal impurities were all 1 ppm or less.
【００２２】[0022]
【実施例２】ＮａＤＰＭに代えて、ＫＤＰＭ（ジピバロ
イルメタナトカリウム）をＹ（ＮＯ3 ）3 と合成したこ
と以外は実施例１と同様にして行い、Ｙ（ＤＰＭ）3 30
ｇを得た。Example 2 The procedure of Example 1 was repeated except that KDPM (dipivaloylmethanato potassium) was synthesized with Y (NO 3 ) 3 in place of NaDPM to obtain Y (DPM) 3 30
g was obtained.
【００２３】得られたＹ（ＤＰＭ）3 については、実施
例１と同様にして金属不純物の含有量を測定した。その
結果、金属不純物としてのＦｅ、Ｃｏ、Ｎｉ、Ｎａまた
はＫは、いずれも１ppm 以下であった。With respect to the obtained Y (DPM) 3 , the content of metal impurities was measured in the same manner as in Example 1. As a result, Fe, Co, Ni, Na or K as metal impurities were all 1 ppm or less.
【００２４】[0024]
【実施例３】ＮａＤＰＭに代えて、ＮａＤＴＭ（ジイソ
ブチルメタナトナトリウム）をＹ（ＮＯ3 ）3 と合成
し、粗結晶（Ｙ（ＤＴＭ）3 ・ＮａＮＯ3 ）を得たこと
以外は実施例１と同様にして行い、Ｙ（ＤＴＭ）3 （ト
リス（ジイソブチルメタナト）イットリウム）28ｇを得
た。Example 3 Instead of NaDPM, NaDTM (sodium diisobutyl methanate) was synthesized with Y (NO 3 ) 3 to obtain a crude crystal (Y (DTM) 3 .NaNO 3 ). In the same manner, 28 g of Y (DTM) 3 (tris (diisobutylmethanato) yttrium) was obtained.
【００２５】得られたＹ（ＤＴＭ）3 については、実施
例１と同様にして金属不純物の含有量を測定した。その
結果、金属不純物としてのＦｅ、Ｃｏ、Ｎｉ、Ｎａまた
はＫは、いずれも１ppm 以下であった。For the obtained Y (DTM) 3 , the content of metal impurities was measured in the same manner as in Example 1. As a result, Fe, Co, Ni, Na or K as metal impurities were all 1 ppm or less.
【００２６】[0026]
【実施例４】Ｙ（ＮＯ3 ）3 に代えて、Ｚｒ（ＮＯ3）
4 をＮａＤＰＭと合成し、粗結晶（Ｚｒ（ＤＰＭ）4 ・
ＮａＮＯ3 ）を得たこと以外は実施例１と同様にして行
い、Ｚｒ（ＤＰＭ）4 （ジピバロイルメタナトジルコニ
ウム）20ｇを得た。Embodiment 4 Instead of Y (NO 3 ) 3 , Zr (NO 3 )
4 was synthesized with NaDPM, and crude crystals (Zr (DPM) 4
Except that NaNO 3 ) was obtained, the same procedure as in Example 1 was carried out to obtain 20 g of Zr (DPM) 4 (dipivaloylmethanatozirconium).
【００２７】得られたＺｒ（ＤＰＭ）4 については、実
施例１と同様にして金属不純物の含有量を測定した。そ
の結果、金属不純物としてのＦｅ、Ｃｏ、Ｎｉ、Ｎａま
たはＫは、いずれも１ppm 以下であった。For the obtained Zr (DPM) 4 , the content of metal impurities was measured in the same manner as in Example 1. As a result, Fe, Co, Ni, Na or K as metal impurities were all 1 ppm or less.
【００２８】[0028]
【実施例５】抽出溶剤をｎ−ヘキサンに代えて、トルエ
ンを使用したこと以外は実施例４と同様にして行い、Ｚ
ｒ（ＤＰＭ）4 22ｇを得た。Example 5 The same procedure as in Example 4 was carried out except that toluene was used instead of n-hexane as the extraction solvent.
There were obtained 22 g of r (DPM) 4 .
【００２９】得られたＺｒ（ＤＰＭ）4 については、実
施例１と同様にして金属不純物の含有量を測定した。そ
の結果、金属不純物としてのＦｅ、Ｃｏ、Ｎｉ、Ｎａま
たはＫは、いずれも１ppm 以下であった。For the obtained Zr (DPM) 4 , the content of metal impurities was measured in the same manner as in Example 1. As a result, Fe, Co, Ni, Na or K as metal impurities were all 1 ppm or less.
【００３０】[0030]
【比較例１】抽出溶剤ｎ−ヘキサンによる抽出工程を省
いたこと以外は実施例１と同様にして行い、Ｙ（ＤＰ
Ｍ）3 28ｇを得た。Comparative Example 1 The procedure of Example 1 was repeated except that the extraction step with the extraction solvent n-hexane was omitted.
M) to obtain a 3 28g.
【００３１】得られたＹ（ＤＰＭ）3 については、実施
例１と同様にして金属不純物の含有量を測定した。その
結果、金属不純物としてのＦｅ、ＣｏおよびＮｉが１pp
m 以下、Ｎａが24ppm およびＫが11ppm であった。With respect to the obtained Y (DPM) 3 , the content of metal impurities was measured in the same manner as in Example 1. As a result, 1 ppm of Fe, Co and Ni as metal impurities
m and below, Na was 24 ppm and K was 11 ppm.
【００３２】[0032]
【比較例２】比較例１で得られたＹ（ＤＰＭ）3 28ｇを
さらに昇華精製（１mmHg、180 ℃、８Hr）を行い、20ｇ
のＹ（ＤＰＭ）3 を得た。Comparative Example 2 28 g of Y (DPM) 3 obtained in Comparative Example 1 was further subjected to sublimation purification (1 mmHg, 180 ° C., 8 hours) to obtain 20 g.
Y (DPM) 3 was obtained.
【００３３】得られたＹ（ＤＰＭ）3 については、実施
例１と同様にして金属不純物の含有量を測定した。その
結果、金属不純物としてのＦｅ、ＣｏおよびＮｉが１pp
m 以下、Ｎａが２ppm およびＫが１ppmであった。With respect to the obtained Y (DPM) 3 , the content of metal impurities was measured in the same manner as in Example 1. As a result, 1 ppm of Fe, Co and Ni as metal impurities
Below m, Na was 2 ppm and K was 1 ppm.
【００３４】[0034]
【発明の効果】本発明の開発により、有機金属錯体にお
ける金属不純物の含有量を、検出限界の１ppm 以下にま
で減少させることができるようになった。また、本発明
は、抽出工程と繰り返し回数の少ない再結晶工程からな
るため、簡便かつ効率良く精製することができる。According to the development of the present invention, the content of metal impurities in the organometallic complex can be reduced to the detection limit of 1 ppm or less. Further, since the present invention comprises an extraction step and a recrystallization step with a small number of repetitions, purification can be performed easily and efficiently.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０７Ｆ 5/00 Ｃ０７Ｆ 5/00 Ｇ 7/00 7/00 Ａ (72)発明者 井野 結理花 東京都千代田区丸の内１丁目８番２号 同和鉱業株式会社内 (56)参考文献 特開 昭53−111017（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 45/79 C07C 45/81 C07C 49/12 C07C 49/14 C07F 5/00 C07F 7/00 Continuation of the front page (51) Int.Cl. 7 Identification code FI C07F 5/00 C07F 5/00 G 7/00 7/00 A (72) Inventor Yuka Ino 1-8-2 Marunouchi, Chiyoda-ku, Tokyo Dowa Mining Co., Ltd. (56) References JP-A-53-111017 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 45/79 C07C 45/81 C07C 49/12 C07C 49/14 C07F 5/00 C07F 7/00
Claims (3)
化合物を配位子とする中心金属元素がIIIA族またはIVA
族金属である有機金属錯体の精製法であって、上記有機
金属錯体の粗結晶を芳香族炭化水素類または脂肪族炭化
水素類に属する抽出溶剤で抽出し、その抽出液から抽出
溶剤を除去して得た結晶物を再結晶精製することを特徴
とする有機金属錯体の精製法。 【化１】 （ただし、式中Ｒ1およびＲ2はそれぞれ独立にメチル
基、イソプロピル基およびｔ−ブチル基からなる群より
選ばれる１種の基を表す。）A central metal element having a 1,3-diketone organic compound represented by the formula 1 as a ligand is a group IIIA or IVA
A method for purifying an organometallic complex which is a group metal, comprising extracting crude crystals of the organometallic complex with an extraction solvent belonging to aromatic hydrocarbons or aliphatic hydrocarbons, and removing the extraction solvent from the extract. A method for purifying an organometallic complex, comprising recrystallizing and purifying a crystal obtained by the above method. Embedded image (Wherein, R 1 and R 2 each independently represent one group selected from the group consisting of a methyl group, an isopropyl group, and a t-butyl group.)
ットリウムまたはジルコニウムである請求項１記載の有
機金属錯体の精製法。2. The method according to claim 1, wherein the central metal element in the metal complex is yttrium or zirconium.
キシレンまたはアルキル基の炭素数が５〜８の脂肪化合
物のうちのいずれか一つである請求項１記載の有機金属
錯体の精製法。3. The method according to claim 1, wherein the extraction solvent is benzene, toluene,
The method for purifying an organometallic complex according to claim 1, wherein the organic metal complex is any one of a fatty compound having 5 to 8 carbon atoms in xylene or an alkyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03059640A JP3117737B2 (en) | 1991-03-01 | 1991-03-01 | Purification method of organometallic complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03059640A JP3117737B2 (en) | 1991-03-01 | 1991-03-01 | Purification method of organometallic complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04275251A JPH04275251A (en) | 1992-09-30 |
| JP3117737B2 true JP3117737B2 (en) | 2000-12-18 |
Family
ID=13119024
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03059640A Expired - Fee Related JP3117737B2 (en) | 1991-03-01 | 1991-03-01 | Purification method of organometallic complex |
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| Country | Link |
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| JP (1) | JP3117737B2 (en) |
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| JPH04275251A (en) | 1992-09-30 |
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