JPH04275251A - Purification of organometallic complex - Google Patents
Purification of organometallic complexInfo
- Publication number
- JPH04275251A JPH04275251A JP5964091A JP5964091A JPH04275251A JP H04275251 A JPH04275251 A JP H04275251A JP 5964091 A JP5964091 A JP 5964091A JP 5964091 A JP5964091 A JP 5964091A JP H04275251 A JPH04275251 A JP H04275251A
- Authority
- JP
- Japan
- Prior art keywords
- organometallic complex
- group
- purifying
- dpm
- extraction solvent
- 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.)
- Granted
Links
- 125000002524 organometallic group Chemical group 0.000 title claims abstract description 38
- 238000000746 purification Methods 0.000 title description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000000605 extraction Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000007824 aliphatic compounds Chemical class 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000010409 thin film Substances 0.000 abstract description 11
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract description 10
- 229910009253 Y(NO3)3 Inorganic materials 0.000 abstract description 5
- 235000010344 sodium nitrate Nutrition 0.000 abstract description 5
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 abstract description 5
- 102100029906 Dolichol-phosphate mannosyltransferase subunit 3 Human genes 0.000 abstract 1
- 101000864172 Homo sapiens Dolichol-phosphate mannosyltransferase subunit 3 Proteins 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 2
- CEGGECULKVTYMM-UHFFFAOYSA-N 2,6-dimethylheptane-3,5-dione Chemical compound CC(C)C(=O)CC(=O)C(C)C CEGGECULKVTYMM-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 inorganic acid salt Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- PRZWBGYJMNFKBT-UHFFFAOYSA-N yttrium Chemical compound [Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y] PRZWBGYJMNFKBT-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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
Abstract
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。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying organometallic complexes used as thin films, superconducting materials, translucent ceramic materials, fuel cell materials, and 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。[Prior Art] Conventionally, two types of methods have been used to form single-crystal thin films and polycrystalline thin films: dry process and wet process, but thin films formed by dry process are better than wet process. At present, dry processes are often used due to their superior 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。Dry processes include physical film-forming methods such as vacuum evaporation, ion plating, and sputtering, and chemical film-forming methods such as chemical vapor deposition (CVD). Among them, the CVD method is widely used because it is suitable for mass production because the film formation rate can be easily controlled, the film does not need to be formed under a high vacuum, and high-speed film formation is possible. In such a CVD method, when a metal thin film is formed by decomposing the vapor of an organometallic complex, a thermal CVD method, a photo CVD method, or a plasma CVD method is employed. Furthermore, in these methods, organometallic complexes in which the organic moiety (ligand) is composed of acetylacetone, dipivaloylmethane, diisobutyrylmethane, or the like are 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 method described above, metal impurities are incorporated into the resulting film-forming material due to the lack of purity of the organometallic complex, which may affect the electrical properties and chemistry of the thin film. There was a problem that it deteriorated the physical properties. Therefore, in conventional technology, the purity of the organometallic complexes used to form metal thin films has been improved by repeatedly subjecting them to direct sublimation purification or recrystallization purification, but these methods are labor-intensive and , countermeasures were required because impurity removal was not complete.
【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。[Problems to be Solved by the Invention] The present invention aims to provide a method for purifying organometallic complexes that can solve the problems of the above-mentioned conventional techniques and easily improve the purity of organometallic complexes. There is.
【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] In order to solve the above problems, the present inventors conducted extensive research and found that the crude crystals of the organometallic complex as a raw material were converted into specific compounds belonging to aromatic hydrocarbons or aliphatic hydrocarbons. It has been discovered that the organometallic complex can be purified to a high degree by recrystallization and purification after extraction with an extraction solvent, and the present invention has been achieved.
【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。[0007] That is, the present invention provides 1,
A method for purifying an organometallic complex having a 3-diketone organic compound as a ligand, the crude crystals of the organometallic complex being extracted with an extraction solvent belonging to aromatic hydrocarbons or aliphatic hydrocarbons, The present invention provides a method for purifying an organometallic complex, which is characterized by recrystallizing and purifying a crystalline product 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 (However, in the formula, R1 and R2 each independently represent one type of 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。[0009] Furthermore, it is more convenient that the central metal element in the organometallic complex belongs to a IIIA metal or an IVA group 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。[0010] Further, the extraction solvent may be benzene, toluene or xylene in the case of aromatic hydrocarbons;
In the case of aliphatic hydrocarbons, it is particularly preferable to use compounds in which the alkyl group has 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 explained in detail as follows. First, an organometallic complex solution is prepared by synthesis from a water-alcohol solution of Na salt or K salt of an organic compound represented by Chemical Formula 3 and a metal inorganic acid salt (chloride, nitrate, or oxynitrate). Next, after removing 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 (However, in the formula, R1 and R2 each independently represent one type of 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。[0013] By extracting the crude crystals of the organometallic complex obtained as described above using an extraction solvent belonging to aromatic hydrocarbons or aliphatic hydrocarbons, a by-product of the organometallic complex is extracted. Inorganic compounds such as inorganic Na salt and inorganic K salt are removed. After the above extraction step, the extraction solvent is removed from the obtained extract to obtain a crystalline substance of the organometallic complex, and the crystalline substance is humidified and dissolved in alcohol, dimethylformamide, or the like. 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。Note that it is sufficient to repeat the recrystallization step in the present invention twice.
【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。[Operation] The greatest feature of the present invention is that an extraction step of aromatic hydrocarbons or aliphatic hydrocarbons with an extraction solvent is provided as a pretreatment for recrystallization purification. By providing the extraction step in this manner, it becomes possible to achieve high purity of the organometallic complex through 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。It is also advantageous according to the invention to use organometallic complexes in which the 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 organometallic complexes of the present invention,
The contents of Fe, Co, Ni, Na, and K as metal impurities are all reduced to below the detection limit of 1 ppm. If the amount of metal impurities contained in the organometallic complex used as a raw material when forming a metal thin film is 1 ppm or less, the electrical and chemical properties of the formed metal thin film will 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。The present invention will now be explained 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（ＤＰＭ）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（１ｍｍ
Ｈｇ、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, Y(NO3)3 and NaDPM(
Coarse crystals of organometallic complexes (Y(DPM)3 ・NaNO3) are synthesized with Y(DPM)3 ・NaNO3
50 g of crude crystals were prepared, and 500 ml of n-hexane was added as an extraction solvent to 50 g of the obtained crude crystals, and the mixture was stirred and dissolved at room temperature to extract Y(DPM)3. Next, the obtained extract was filtered under pressure (3KG) and then heated under reduced pressure (1mm
n-hexane in the extract was removed to obtain 35 g of crystalline Y(DPM)3 (dipivaloylmethanatoyttrium).
【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 crystalline product was dissolved in dimethylformamide by heating and then left at room temperature, which was repeated twice to obtain a recrystallized product. Thereafter, the recrystallized product was dried under reduced pressure by heating to obtain 28 g of a highly pure 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。Y(DPM)3 thus obtained
The impurity content was measured. In the measurement, metal impurities were measured by ICP using a sample prepared by dissolving the obtained Y(DPM)3 in aqua regia. As a result, the amount of Fe, Co, Ni, Na, or K as metal impurities was 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 ３０ｇを得た。[Example 2] The procedure was carried out in the same manner as in Example 1 except that KDPM (dipivaloylmethanatopotassium) was synthesized with Y(NO3)3 instead of NaDPM, and Y(DPM)
3 30g 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。Regarding the obtained Y(DPM)3, the content of metal impurities was measured in the same manner as in Example 1. As a result, the amount of Fe, Co, Ni, Na, or K as metal impurities was 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] The procedure was the same as in Example 1 except that NaDTM (sodium diisobutylmethanato) was synthesized with Y(NO3)3 instead of NaDPM to obtain crude crystals (Y(DTM)3 .NaNO3). Y(DTM)
3 (tris(diisobutylmethanato)yttrium)
28g 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。Regarding the obtained Y(DTM)3, the content of metal impurities was measured in the same manner as in Example 1. As a result, the amount of Fe, Co, Ni, Na, or K as metal impurities was 1 ppm or less.
【００２６】[0026]
【実施例４】Ｙ（ＮＯ３ ）３ に代えて、Ｚｒ（ＮＯ
３）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。[Example 4] Instead of Y(NO3)3, Zr(NO3)
3) Synthesize 4 with NaDPM to obtain crude crystals (Zr(DPM)
)4 .NaNO3 ) was carried out in the same manner as in Example 1, 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。Regarding 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 as metal impurities
In both cases, K was 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 procedure was carried out in the same manner as in Example 4 except that toluene was used instead of n-hexane as the extraction solvent.
22 g of r(DPM)4 was obtained.
【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。Regarding 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 as metal impurities
In both cases, K was 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（ＤＰＭ
）３ ２８ｇを得た。[Comparative Example 1] The procedure was carried out in the same manner as in Example 1 except that the extraction step using the extraction solvent n-hexane was omitted.
)3 28g was obtained.
【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１
ｐｐｍ 以下、Ｎａが２４ｐｐｍ およびＫが１１ｐｐ
ｍ であった。Regarding 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 and Ni as metal impurities are 1
ppm below, Na is 24ppm and K is 11ppm
It was m.
【００３２】[0032]
【比較例２】比較例１で得られたＹ（ＤＰＭ）３ ２８
ｇ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] Y(DPM)328 obtained in Comparative Example 1
Further purification by sublimation (1 mmHg, 180 °C, 8 Hr)
) to obtain 20 g of Y(DPM)3.
【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１
ｐｐｍ 以下、Ｎａが２ｐｐｍ およびＫが１ｐｐｍで
あった。Regarding 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 and Ni as metal impurities are 1
ppm below, 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。[Effects of the Invention] Through the development of the present invention, it has become possible to reduce the content of metal impurities in organometallic complexes to below the detection limit of 1 ppm. Moreover, since the present invention consists of an extraction step and a recrystallization step with a small number of repetitions, purification can be performed simply and efficiently.
Claims (3)
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。 【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。）1. A method for purifying an organometallic complex using a 1,3-diketone organic compound represented by formula 1 as a ligand, wherein the crude crystals of the organometallic complex are purified by aromatic hydrocarbons or aliphatic hydrocarbons. 1. A method for purifying an organometallic complex, which comprises extracting with an extraction solvent belonging to hydrocarbons, and recrystallizing and purifying the crystalline product obtained by removing the extraction solvent from the extract. embedded image (However, in the formula, R1 and R2 each independently represent one type of group selected from the group consisting of a methyl group, an isopropyl group, and a t-butyl group.)
素が ＩＩＩＡ族金属またはＩＶＡ族金属に属するもの
である請求項１記載の有機金属錯体の精製法。2. The method for purifying an organometallic complex according to claim 1, wherein the central metal element in the organometallic complex belongs to a group IIIA metal or a group IVA metal.
、キシレンまたはアルキル基の炭素数が５〜８の脂肪族
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 for purifying an organometallic complex according to claim 1, wherein the extraction solvent is one of benzene, toluene, xylene, or an aliphatic compound in which an alkyl group has 5 to 8 carbon atoms.
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 true JPH04275251A (en) | 1992-09-30 |
| JP3117737B2 JP3117737B2 (en) | 2000-12-18 |
Family
ID=13119024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03059640A Expired - Fee Related JP3117737B2 (en) | 1991-03-01 | 1991-03-01 | Purification method of organometallic complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3117737B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1712656A1 (en) * | 2005-04-12 | 2006-10-18 | Rohm and Haas Electronic Materials, L.L.C. | Metal-containing compound purification |
-
1991
- 1991-03-01 JP JP03059640A patent/JP3117737B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1712656A1 (en) * | 2005-04-12 | 2006-10-18 | Rohm and Haas Electronic Materials, L.L.C. | Metal-containing compound purification |
| CN100408589C (en) * | 2005-04-12 | 2008-08-06 | 罗门哈斯电子材料有限公司 | Purification of metal-containing compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3117737B2 (en) | 2000-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100391753B1 (en) | Synthesis of 4-acetoxy-2? -Benzoyloxy-5?, 2O-epoxy-1,7 ?, 10? -Trihydroxy-9-oxo-tax- Preparation of butoxycarbonylamino-2-hydroxy-3-phenylpropionate trihydrate | |
| EP1027358B1 (en) | Anhydrous mononuclear tris(beta-diketonate) bismuth compositions for deposition of bismuth-containing films, and method of making the same | |
| Song et al. | Synthesis and characterization of volatile metal β-diketonate chelates of M (DPM) n (M= Ce, Gd, Y, Zr, n= 3, 4) used as precursors for MOCVD | |
| Fleeting et al. | Developing the Chemistry of Novel Scandium β‐Diketonates for the MOCVD of Scandium‐Containing Oxides | |
| US7678356B2 (en) | Process for the preparation of crystalline magnesium borohydride | |
| JPH04275251A (en) | Purification of organometallic complex | |
| Frauenhoff et al. | Isolation, characterization, and substitution reactions of the osmium trinuclear triflate complex H2Os3 (CO) 9 (O3SCF3) 2. X-ray crystal structure of the mixed oxyligand cluster (. mu.-H) 2Os3 (CO) 9 (. mu.,. eta. 2-O2CCH3)(. eta. 1-O3SCF3) | |
| Wilson et al. | Structure of chloronitrosyl (. eta. 2-sulfur dioxide) bis (triphenylphosphine) ruthenium-Dichloromethane, RuCl (NO)(. eta. 2-SO2)(P (C6H5) 3) 2. CH2Cl2 | |
| JP3981520B2 (en) | Method for separating organic compounds | |
| Cotton et al. | A quadruply bonded dimolybdenum compound with bridging pyrimidinethiol ligands | |
| Adams et al. | Cluster synthesis. 34. Unsaturation in a high-nuclearity platinum-osmium carbonyl cluster complex. Studies of the synthesis, structure, and reactivity of Pt2Os4 (CO) 11 (COD) 2 | |
| Sturgeon et al. | Synthesis and characterization of a high-nuclearity cluster with a (. mu. 4-oxo) tetracobalt (II) core | |
| Chang et al. | A novel method for the preparation of uranium complexes via electrolytic amalgamation | |
| Ibragimov et al. | Inclusion complexes of the natural product gossypol. The formation of different gossypol polymorphs on decomposition of channel type inclusion complexes | |
| JP2543016B2 (en) | Method for producing 1,3-diketone-based organometallic complex | |
| JPS5830289B2 (en) | Synquiterpenophenol | |
| JP4767158B2 (en) | Method for producing bis (pentamethylcyclopentadienyl) strontium | |
| CN113666892B (en) | New crystal form of englitz intermediate and preparation method thereof | |
| KR102548034B1 (en) | Novel Organo-Bismuth Compounds, Preparation method thereof, and Method for deposition of thin film using the same | |
| JP4086219B2 (en) | High purity bismuth tris (β-diketonate) and method for producing the same | |
| JP2551097B2 (en) | Method for dehydrating metal halides | |
| JP2002249455A (en) | METHOD FOR PRODUCING HIGH PURITY HAFNIUM COMPLEX Hf(DPM)4 | |
| CN116239538A (en) | New lopinavir crystal form and preparation method thereof | |
| JP2002249456A (en) | METHOD FOR PRODUCING HIGH PURITY ZIRCONIUM COMPLEX Zr(DPM)2(i-C3H7O)2 | |
| JPS63227593A (en) | Production of metal alkoxide solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071006 Year of fee payment: 7 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071006 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081006 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091006 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |