JP2012214394A - Platinum binuclear complex, method for producing the same, catalysis using the same, and precursor of platinum nanoparticle carrying catalyst - Google Patents
Platinum binuclear complex, method for producing the same, catalysis using the same, and precursor of platinum nanoparticle carrying catalyst Download PDFInfo
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本発明は、白金二核錯体、その製造方法、それを用いた触媒及び白金ナノ粒子担持触媒の前駆体に関する。 The present invention relates to a platinum binuclear complex, a production method thereof, a catalyst using the same, and a precursor of a platinum nanoparticle-supported catalyst.
担持白金触媒の白金粒子の微細化を目的として、前駆体としての白金複核錯体が注目されている。これまで、白金の複核錯体としては、［Ｐｔ３（ＣＯ）６］ｎ（ｎ＝１〜６，１０）（例えば、非特許文献１を参照。）、［Ｐｔ３（ＣＯ）６］ｎ（ｎ＝２〜５）（例えば、非特許文献２を参照。）、［Ｐｔ（ＣＯ）２］ｎ（ｎ＝３，６，９）（例えば、非特許文献３を参照。）、［Ｐｔ１９（ＣＯ）２２］（例えば、非特許文献４を参照。）、［Ｐｔ２４（ＣＯ）３０］（例えば、非特許文献４を参照。）、［Ｐｔ２６（ＣＯ）３２］（例えば、非特許文献５を参照。）、［Ｐｔ３８（ＣＯ）４４］（例えば、非特許文献６を参照。）型のカルボニル錯体の合成が報告されている。白金（ＩＩＩ）−白金（ＩＩＩ）結合を有する白金二核錯体の合成が報告されている（例えば、非特許文献７を参照。）。また、白金−白金結合を有する白金多核錯体については、イソシアニドが配位した、三核錯体又は七核錯体の合成が報告されている（例えば、非特許文献８〜１０を参照。）。 For the purpose of making the platinum particles of the supported platinum catalyst finer, a platinum binuclear complex as a precursor has attracted attention. To date, platinum complex complexes include [Pt 3 (CO) 6 ] n (n = 1 to 6,10) (see, for example, Non-Patent Document 1), [Pt 3 (CO) 6 ] n ( n = 2 to 5) (for example, refer to Non-Patent Document 2), [Pt (CO) 2 ] n (n = 3, 6, 9) (for example, refer to Non-Patent Document 3), [Pt 19 (CO) 22 ] (for example, see Non-Patent Document 4), [Pt 24 (CO) 30 ] (for example, see Non-Patent Document 4), [Pt 26 (CO) 32 ] (for example, Non-Patent Document 4) Reference 5), and [Pt 38 (CO) 44 ] (see, for example, Non-Patent Document 6) type carbonyl complexes have been reported. Synthesis of a platinum binuclear complex having a platinum (III) -platinum (III) bond has been reported (for example, see Non-Patent Document 7). Moreover, about the platinum polynuclear complex which has a platinum-platinum bond, the synthesis | combination of the trinuclear complex or the heptanuclear complex which isocyanide coordinated has been reported (for example, refer nonpatent literature 8-10).
白金（Ｉ）−白金（Ｉ）結合を有する二核錯体は、これまで知られていない。 A binuclear complex having a platinum (I) -platinum (I) bond has not been known so far.
本発明の目的は、白金（Ｉ）−白金（Ｉ）結合を有する新規な白金二核錯体を提供すること及びその製造方法を提供することである。また、本発明の別の目的は、新規な白金二核錯体を用いた均一系白金錯体触媒を提供することである。本発明の別の目的は、白金ナノ粒子担持触媒の前駆体を提供することである。 An object of the present invention is to provide a novel platinum binuclear complex having a platinum (I) -platinum (I) bond and a method for producing the same. Another object of the present invention is to provide a homogeneous platinum complex catalyst using a novel platinum binuclear complex. Another object of the present invention is to provide a precursor of a platinum nanoparticle supported catalyst.
本発明に係る白金二核錯体は、一般式（化１）で表され、白金（Ｉ）と白金（Ｉ）との結合を有する。
（化１）［Ｐｔ２Ｘ２Ｌ１ ４］
一般式（化１）において、Ｘはハロゲン原子、Ｌ１は構成元素として炭素、水素及び窒素からなる中性配位子を示す。
The platinum binuclear complex according to the present invention is represented by the general formula (Formula 1) and has a bond between platinum (I) and platinum (I).
(Chemical formula 1) [Pt 2 X 2 L 1 4 ]
In the general formula (Formula 1), X represents a halogen atom, and L 1 represents a neutral ligand composed of carbon, hydrogen and nitrogen as constituent elements.
本発明に係る白金二核錯体の製造方法は、一般式（化２）で表される白金単核錯体と構成元素として炭素、水素及び窒素からなる中性配位子Ｌ１とを反応させて、一般式（化３）で表される白金単核錯体を得る工程１と、一般式（化３）で表される白金単核錯体を、ハロゲン引き抜き能を有するＰｔ（ＩＩ）からＰｔ（Ｉ）への１電子還元剤を用いて還元し、一般式（化１）で表される白金二核錯体を得る工程２とを有することを特徴とする。
（化２）［ＰｔＸ２Ｌ２］
一般式（化２）において、Ｘはハロゲン原子、Ｌ２は中性配位子を示す。
（化３）［ＰｔＸ２Ｌ１ ２］
一般式（化３）において、Ｘはハロゲン原子、Ｌ１は構成元素として炭素、水素及び窒素からなる中性配位子を示す。
The method for producing a platinum binuclear complex according to the present invention comprises reacting a platinum mononuclear complex represented by the general formula (Chemical Formula 2) with a neutral ligand L 1 composed of carbon, hydrogen and nitrogen as constituent elements. Step 1 for obtaining a platinum mononuclear complex represented by the general formula (Chemical Formula 3) and a platinum mononuclear complex represented by the general formula (Chemical Formula 3) from Pt (II) having a halogen abstraction ability to Pt (I And a step 2 of obtaining a platinum binuclear complex represented by the general formula (Chemical Formula 1).
(Chemical Formula 2) [PtX 2 L 2 ]
In the general formula (Formula 2), X represents a halogen atom, and L 2 represents a neutral ligand.
(Chemical formula 3) [PtX 2 L 1 2 ]
In the general formula (Formula 3), X represents a halogen atom, and L 1 represents a neutral ligand composed of carbon, hydrogen and nitrogen as constituent elements.
本発明に係る白金二核錯体の製造方法では、前記１電子還元剤が、リチウム、ナトリウム、カリウム又はマグネシウムのうちの少なくとも１種である形態を包含する。 In the method for producing a platinum binuclear complex according to the present invention, the one-electron reducing agent includes at least one of lithium, sodium, potassium or magnesium.
本発明に係る均一系白金錯体触媒は、本発明に係る白金二核錯体を含有する。 The homogeneous platinum complex catalyst according to the present invention contains the platinum binuclear complex according to the present invention.
本発明に係る白金ナノ粒子担持触媒の前駆体は、本発明に係る白金二核錯体を、多孔質担持体に担持させてなる。 The platinum nanoparticle-supported catalyst precursor according to the present invention is obtained by supporting the platinum binuclear complex according to the present invention on a porous support.
本発明は、白金（Ｉ）−白金（Ｉ）結合を有する白金二核錯体を提供すること及びその製造方法を提供することができる。本発明は、新規な白金二核錯体を用いた均一系白金錯体触媒を提供することができる。本発明は、白金ナノ粒子担持触媒の前駆体を提供することができる。 The present invention can provide a platinum binuclear complex having a platinum (I) -platinum (I) bond and a method for producing the same. The present invention can provide a homogeneous platinum complex catalyst using a novel platinum binuclear complex. The present invention can provide a precursor of a platinum nanoparticle-supported catalyst.
次に、本発明について実施形態を示して詳細に説明するが本発明はこれらの記載に限定して解釈されない。本発明の効果を奏する限り、実施形態は種々の変形をしてもよい。 Next, the present invention will be described in detail with reference to embodiments, but the present invention is not construed as being limited to these descriptions. As long as the effect of the present invention is exhibited, the embodiment may be variously modified.
本実施形態に係る白金二核錯体は、一般式（化１）で表され、白金（Ｉ）と白金（Ｉ）との結合を有する。
（化１）［Ｐｔ２Ｘ２Ｌ１ ４］
一般式（化１）において、Ｘはハロゲン原子、Ｌ１は構成元素として炭素、水素及び窒素からなる中性配位子を示す。
The platinum binuclear complex according to this embodiment is represented by the general formula (Formula 1), and has a bond between platinum (I) and platinum (I).
(Chemical formula 1) [Pt 2 X 2 L 1 4 ]
In the general formula (Formula 1), X represents a halogen atom, and L 1 represents a neutral ligand composed of carbon, hydrogen and nitrogen as constituent elements.
一般式（化１）において、Ｘは、ハロゲン原子である。ハロゲン原子は、フッ素（Ｆ）、塩素（Ｃｌ）、臭素（Ｂｒ）又はヨウ素（Ｉ）である。この中で、ヨウ素がより好ましい。 In the general formula (Formula 1), X is a halogen atom. The halogen atom is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I). Among these, iodine is more preferable.
一般式（化１）において、Ｌ１は、構成元素として炭素（Ｃ）、水素（Ｈ）及び窒素（Ｎ）からなる中性配位子である。Ｌ１としては、例えば、イソシアニド類、ピリジン類、ニトリル類、アミン類、イミン類である。この中で、イソシアニド類がより好ましい。イソシアニド類は、例えば、２，６‐ジメチルフェニルイソシアニド、２，３‐ジメチルフェニルイソシアニド、２，４‐ジメチルフェニルイソシアニド、２，５‐ジメチルフェニルイソシアニド、３，４‐ジメチルフェニルイソシアニド、３，５‐ジメチルフェニルイソシアニド、メチルイソシアニド、エチルイソシアニド、プロピルイソシアニド、ノルマルブチルイソシアニド、ターシャリーブチルイソシアニド、ペンチルイソシアニド、ヘキシルイソシアニド、シクロヘキシルイソシアニド、フェニルイソシアニド、トリフルオロメチルイソシアニド、トルエンスルホニルメチルイソシアニドである。この中で、２，６‐ジメチルフェニルイソシアニドが特に好ましい。 In the general formula (Formula 1), L 1 is a neutral ligand composed of carbon (C), hydrogen (H), and nitrogen (N) as constituent elements. Examples of L 1 include isocyanides, pyridines, nitriles, amines, and imines. Of these, isocyanides are more preferred. Isocyanides include, for example, 2,6-dimethylphenyl isocyanide, 2,3-dimethylphenyl isocyanide, 2,4-dimethylphenyl isocyanide, 2,5-dimethylphenyl isocyanide, 3,4-dimethylphenyl isocyanide, 3,5- Dimethylphenyl isocyanide, methyl isocyanide, ethyl isocyanide, propyl isocyanide, normal butyl isocyanide, tertiary butyl isocyanide, pentyl isocyanide, hexyl isocyanide, cyclohexyl isocyanide, phenyl isocyanide, trifluoromethyl isocyanide, toluenesulfonylmethyl isocyanide. Of these, 2,6-dimethylphenyl isocyanide is particularly preferred.
一般式（化１）において、Ｐｔ（白金）の酸化数は、１である。一般式（化１）で表される化合物は、Ｐｔ（Ｉ）とＰｔ（Ｉ）との間に結合を有する。白金二核錯体が、白金（Ｉ）−白金（Ｉ）結合を有すると、白金（ＩＩＩ）−白金（ＩＩＩ）結合を有する錯体と比較して、活性が高く、触媒としての性能が向上する。結果として、得られるナノ微粒子の粒子径をより小さくでき、担持体に担持させやすくなるので、均一系錯体触媒として、又は、アルミナ、シリカ、チタニア、カーボンなどの多孔質担体への担持処理によって、白金ナノ粒子担持触媒の前駆体として応用できる。 In the general formula (Formula 1), the oxidation number of Pt (platinum) is 1. The compound represented by the general formula (Formula 1) has a bond between Pt (I) and Pt (I). When the platinum binuclear complex has a platinum (I) -platinum (I) bond, the activity is higher than that of the complex having a platinum (III) -platinum (III) bond, and the performance as a catalyst is improved. As a result, the particle size of the resulting nano fine particles can be made smaller and easily supported on the support, so that it is supported as a homogeneous complex catalyst or by a support treatment on a porous carrier such as alumina, silica, titania, carbon, etc. It can be applied as a precursor of platinum nanoparticle supported catalyst.
一般式（化１）で表される白金二核錯体の製造方法は、一般式（化２）で表される白金単核錯体と構成元素として炭素、水素及び窒素からなる中性配位子Ｌ１とを反応させて、一般式（化３）で表される白金単核錯体を得る工程１と、一般式（化３）で表される白金単核錯体を、ハロゲン引き抜き能を有するＰｔ（ＩＩ）からＰｔ（Ｉ）への１電子還元剤を用いて還元し、一般式（化１）で表される白金二核錯体を得る工程２とを有する。
（化２）［ＰｔＸ２Ｌ２］
一般式（化２）において、Ｘはハロゲン原子、Ｌ２は中性配位子を示す。
（化３）［ＰｔＸ２Ｌ１ ２］
一般式（化３）において、Ｘはハロゲン原子、Ｌ１は構成元素として炭素、水素及び窒素からなる中性配位子を示す。
The method for producing a platinum binuclear complex represented by the general formula (Chemical Formula 1) is a neutral ligand L composed of a platinum mononuclear complex represented by the general formula (Chemical Formula 2) and carbon, hydrogen and nitrogen as constituent elements. 1 is reacted to obtain a platinum mononuclear complex represented by the general formula (Chemical Formula 3), and the platinum mononuclear complex represented by the general formula (Chemical Formula 3) is converted to Pt ( And II using a one-electron reducing agent from Pt (I) to obtain a platinum binuclear complex represented by the general formula (Chemical Formula 1).
(Chemical Formula 2) [PtX 2 L 2 ]
In the general formula (Formula 2), X represents a halogen atom, and L 2 represents a neutral ligand.
(Chemical formula 3) [PtX 2 L 1 2 ]
In the general formula (Formula 3), X represents a halogen atom, and L 1 represents a neutral ligand composed of carbon, hydrogen and nitrogen as constituent elements.
一般式（化２）において、Ｘは、ハロゲン原子であり、一般式（化１）におけるハロゲン原子と同じである。 In the general formula (Chemical Formula 2), X is a halogen atom, which is the same as the halogen atom in the general formula (Chemical Formula 1).
一般式（化２）において、Ｌ２は、中性配位子である。Ｌ２としては、例えば、１，５‐シクロオクタジエン（ｃｏｄ）、シクロオクテン（ｃｏｅ）である。この中で、１，５‐シクロオクタジエンがより好ましい。 In the general formula (Formula 2), L 2 is a neutral ligand. L 2 is, for example, 1,5-cyclooctadiene (cod) or cyclooctene (coe). Of these, 1,5-cyclooctadiene is more preferred.
一般式（化２）で表される化合物は、例えば、ジヨード（１，５‐シクロオクタジエン）プラチニウム（ＩＩ）、ジクロロ（１，５‐シクロオクタジエン）プラチニウム（ＩＩ）、ジブロモ（１，５‐シクロオクタジエン）プラチニウム（ＩＩ）、ジヨード（シクロオクテン）プラチニウム（ＩＩ）、ジクロロ（シクロオクテン）プラチニウム（ＩＩ）、ジブロモ（シクロオクテン）プラチニウム（ＩＩ）である。 The compound represented by the general formula (Chemical Formula 2) is, for example, diiodo (1,5-cyclooctadiene) platinium (II), dichloro (1,5-cyclooctadiene) platinium (II), dibromo (1,5 -Cyclooctadiene) platinium (II), diiodo (cyclooctene) platinium (II), dichloro (cyclooctene) platinium (II), dibromo (cyclooctene) platinium (II).
工程１について説明する。工程１は、一般式（化２）で表される白金単核錯体と中性配位子Ｌ１とを反応させて、一般式（化３）で表される白金単核錯体を合成する工程である。一般式（化２）で表される白金単核錯体と中性配位子Ｌ１との反応は、両者を接触させて、一般式（化２）で表される白金単核錯体が有する中性配位子Ｌ２を中性配位子Ｌ１と置換する反応である。その反応条件は、特に制限はないが、通常は、一般式（化２）で表される白金単核錯体と中性配位子Ｌ１とを、反応溶媒の存在下で、２０〜４０℃で、０．５〜２４時間、攪拌することで反応を行うことができる。一般式（化２）で表される白金単核錯体、中性配位子Ｌ１及び反応溶媒を反応容器内に添加する順は、特に限定されず、例えば、一般式（化２）で表される白金単核錯体及び中性配位子Ｌ１を添加後、反応溶媒を添加する形態、一般式（化２）で表される白金単核錯体、中性配位子Ｌ１及び反応溶媒を同時に添加する形態、反応溶媒を添加後、一般式（化２）で表される白金単核錯体及び中性配位子Ｌ１を添加する形態である。 Step 1 will be described. Step 1, general formula (2) in with the platinum mononuclear complex and a neutral ligand L 1 is reacted represented, to synthesize a platinum mononuclear complex represented by the general formula (3) Step It is. The reaction between the platinum mononuclear complex represented by the general formula (Chemical Formula 2) and the neutral ligand L 1 is carried out by bringing the platinum mononuclear complex represented by the general formula (Chemical Formula 2) into contact with each other. This is a reaction to replace the neutral ligand L 2 with the neutral ligand L 1 . The reaction conditions are not particularly limited. Usually, the platinum mononuclear complex represented by the general formula (Chemical Formula 2) and the neutral ligand L 1 are 20 to 40 ° C. in the presence of a reaction solvent. The reaction can be carried out by stirring for 0.5 to 24 hours. The order of adding the platinum mononuclear complex represented by the general formula (Chemical Formula 2), the neutral ligand L 1 and the reaction solvent into the reaction vessel is not particularly limited. For example, the order is represented by the general formula (Chemical Formula 2). After adding the platinum mononuclear complex and the neutral ligand L 1 , the form in which the reaction solvent is added, the platinum mononuclear complex represented by the general formula (Formula 2), the neutral ligand L 1 and the reaction solvent Are added simultaneously, and after adding the reaction solvent, the platinum mononuclear complex represented by the general formula (Formula 2) and the neutral ligand L 1 are added.
使用可能な反応溶媒は、例えば、テトラヒドロフラン（ＴＨＦ）、クロロホルム、ジクロロメタン、ジクロロエタン、ジエチルエーテルである。これらは、１種を単独で使用するか、又は２種以上を併用することができる。この中で、テトラヒドロフラン、ジクロロメタンがより好ましい。 Usable reaction solvents are, for example, tetrahydrofuran (THF), chloroform, dichloromethane, dichloroethane, diethyl ether. These can be used individually by 1 type or can use 2 or more types together. Of these, tetrahydrofuran and dichloromethane are more preferred.
一般式（化２）で表される白金単核錯体と中性配位子Ｌ１との比率は、化学量論比よりも中性配位子Ｌ１の使用量が多ければ特に制限なく、中性配位子Ｌ１の使用量が、一般式（化２）で表される白金単核錯体１当量に対して、２．０〜２．４当量であることが好ましい。より好ましくは、２．１〜２．３当量である。 The ratio between the platinum mononuclear complex represented by the general formula (Chemical Formula 2) and the neutral ligand L 1 is not particularly limited as long as the used amount of the neutral ligand L 1 is larger than the stoichiometric ratio. the amount of neutral ligands L 1 are, with respect to the general formula (formula 2) platinum mononuclear complex 1 equivalent represented by is preferably 2.0 to 2.4 equivalents. More preferably, it is 2.1 to 2.3 equivalents.
一般式（化２）で表される白金単核錯体と中性配位子Ｌ１との反応は、不活性ガス雰囲気下で行うことが好ましい。不活性ガスは、例えば、アルゴンガス、窒素ガスである。 The reaction between the platinum mononuclear complex represented by the general formula (Chemical Formula 2) and the neutral ligand L 1 is preferably performed in an inert gas atmosphere. The inert gas is, for example, argon gas or nitrogen gas.
一般式（化３）で表される白金単核錯体は、通常、反応後の反応液に溶解している。そこで、反応液を濾過して不溶物を除去し、濾液を濃縮すると、一般式（化３）で表される白金単核錯体が析出し、反応溶媒を洗浄、乾燥などによって除去することで、一般式（化３）で表される白金単核錯体を得ることができる。さらに、必要に応じて、再結晶法、カラムクロマトグラフィー法などの公知の精製手段を行って、生成してもよい。 The platinum mononuclear complex represented by the general formula (Chemical Formula 3) is usually dissolved in the reaction solution after the reaction. Therefore, the reaction solution is filtered to remove insoluble matters, and the filtrate is concentrated, whereby a platinum mononuclear complex represented by the general formula (Chemical Formula 3) is precipitated, and the reaction solvent is removed by washing, drying, etc. A platinum mononuclear complex represented by the general formula (Formula 3) can be obtained. Furthermore, it may be produced by performing known purification means such as a recrystallization method and a column chromatography method, if necessary.
一般式（化３）で表される白金単核錯体は、一般式（化１）で表される白金二核錯体の前駆体として有用である。一般式（化３）において、Ｐｔ（白金）の酸化数は、２である。一般式（化３）で表される白金単核錯体は、正方平面型の立体構造を有することが好ましい。 The platinum mononuclear complex represented by the general formula (Chemical Formula 3) is useful as a precursor of the platinum binuclear complex represented by the general formula (Chemical Formula 1). In the general formula (Formula 3), the oxidation number of Pt (platinum) is 2. The platinum mononuclear complex represented by the general formula (Chemical Formula 3) preferably has a tetragonal planar type three-dimensional structure.
工程２について説明する。工程２では、一般式（化３）で表される白金単核錯体を酸化還元反応によって還元して、一般式（化１）で表される白金二核錯体を合成する工程である。その反応条件は、特に制限はないが、通常は、一般式（化３）で表される白金単核錯体とハロゲン引き抜き能を有するＰｔ（ＩＩ）からＰｔ（Ｉ）への１電子還元剤とを、反応溶媒の存在下で、２０〜４０℃で、４〜７２時間、攪拌することで反応させることができる。１電子還元剤は、ハロゲン引き抜き能を有するＰｔ（ＩＩ）からＰｔ（Ｉ）への１電子還元剤であり、リチウム（Ｌｉ）、ナトリウム（Ｎａ）、カリウム（Ｋ）又はマグネシウム（Ｍｇ）のうちの少なくとも１種であることが好ましい。より好ましくは、マグネシウム（Ｍｇ）である。反応溶媒は、工程１で使用可能な反応溶媒として例示したものを使用でき、その中でも、ジクロロメタンとテトラヒドロフランとの混合溶媒がより好ましい。 Step 2 will be described. Step 2 is a step of synthesizing a platinum binuclear complex represented by the general formula (Chemical Formula 1) by reducing the platinum mononuclear complex represented by the general formula (Chemical Formula 3) by an oxidation-reduction reaction. The reaction conditions are not particularly limited, but usually a platinum mononuclear complex represented by the general formula (Chemical Formula 3) and a one-electron reducing agent from Pt (II) to Pt (I) having a halogen extracting ability Can be reacted by stirring at 20 to 40 ° C. for 4 to 72 hours in the presence of a reaction solvent. The one-electron reducing agent is a one-electron reducing agent from Pt (II) to Pt (I) having a halogen-extracting ability. Among lithium (Li), sodium (Na), potassium (K), and magnesium (Mg) It is preferable that it is at least 1 type of these. More preferably, it is magnesium (Mg). What was illustrated as a reaction solvent which can be used at the process 1 can be used for the reaction solvent, Among these, the mixed solvent of a dichloromethane and tetrahydrofuran is more preferable.
還元剤としてのマグネシウムの使用量は、一般式（化３）で表される白金単核錯体１当量に対して、８．０〜１００．０当量であることが好ましい。より好ましくは、１０．０〜１００．０当量である。 The amount of magnesium used as the reducing agent is preferably 8.0 to 100.0 equivalents relative to 1 equivalent of the platinum mononuclear complex represented by the general formula (Formula 3). More preferably, it is 10.0-100.0 equivalent.
酸化還元反応は、不活性ガス雰囲気下又は空気下で行うことが好ましい。不活性ガスは、工程１で説明したとおりである。 The oxidation-reduction reaction is preferably performed in an inert gas atmosphere or air. The inert gas is as described in step 1.
一般式（化１）で表される白金二核錯体は、通常、反応後の反応液に溶解している。そこで、反応液を濾過して不溶物を除去し、濾液を濃縮すると、一般式（化１）で表される白金二核錯体が析出し、反応溶媒を洗浄、乾燥などによって除去することで、一般式（化１）で表される白金二核錯体を得ることができる。さらに、必要に応じて、再結晶法、カラムクロマトグラフィー法などの公知の精製手段を行って、生成してもよい。 The platinum binuclear complex represented by the general formula (Chemical Formula 1) is usually dissolved in the reaction solution after the reaction. Then, the reaction solution is filtered to remove insoluble matters, and the filtrate is concentrated, whereby a platinum binuclear complex represented by the general formula (Chemical Formula 1) is precipitated, and the reaction solvent is removed by washing, drying, etc. A platinum binuclear complex represented by the general formula (Formula 1) can be obtained. Furthermore, it may be produced by performing known purification means such as a recrystallization method and a column chromatography method, if necessary.
本実施形態に係る均一系白金錯体触媒は、一般式（化１）で表される白金二核錯体を含有する。均一系白金錯体触媒は、オレフィンの水素化反応、不飽和結合の水素化反応、ヒドロキシル化反応、ヒドロシリル化反応又はヒドロホスフィン化反応に適している。 The homogeneous platinum complex catalyst according to this embodiment contains a platinum binuclear complex represented by the general formula (Formula 1). The homogeneous platinum complex catalyst is suitable for olefin hydrogenation reaction, unsaturated bond hydrogenation reaction, hydroxylation reaction, hydrosilylation reaction or hydrophosphination reaction.
本実施形態に係る白金ナノ粒子担持触媒の前駆体は、一般式（化１）で表される白金二核錯体を、多孔質担持体に担持させてなる。多孔質担持体は、特に限定されず、例えば、アルミナ、シリカ、チタニア、カーボンである。多孔質担持体に担持させる方法は、特に限定されず、例えば、一般式（化１）で表される白金二核錯体を、多孔質担持体に結合させて担持する形態、一般式（化１）で表される白金二核錯体を、多孔質担持体の孔内又は表面に付着させて担持する形態である。 The platinum nanoparticle-supported catalyst precursor according to this embodiment is obtained by supporting a platinum binuclear complex represented by the general formula (Formula 1) on a porous support. The porous carrier is not particularly limited, and examples thereof include alumina, silica, titania, and carbon. The method for supporting the porous carrier is not particularly limited. For example, a form in which a platinum binuclear complex represented by the general formula (Chemical Formula 1) is bonded to the porous carrier and supported is represented by the general formula (Chemical Formula 1). The platinum binuclear complex represented by (1) is supported while adhering to the inside or the surface of the porous support.
一般式（化１）で表される白金二核錯体を、多孔質担持体に担持させた白金ナノ粒子担持触媒の前駆体を焼成すると、白金二核錯体が白金ナノ粒子となり、白金ナノ粒子担持触媒が得られる。この白金ナノ粒子担持触媒は、排ガス浄化触媒として利用できる。 When a platinum nanoparticle-supported catalyst precursor in which a platinum binuclear complex represented by the general formula (Chemical Formula 1) is supported on a porous carrier is calcined, the platinum binuclear complex becomes platinum nanoparticles, and platinum nanoparticles are supported. A catalyst is obtained. This platinum nanoparticle-supported catalyst can be used as an exhaust gas purification catalyst.
次に、実施例を示しながら本発明についてさらに詳細に説明するが、本発明は実施例に限定して解釈されない。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not construed as being limited to the examples.
＜実施例１＞
（工程１）
アルゴン雰囲気下で、５００ｍｌのシュレンク容器に一般式（化２）で表される白金単核錯体として、ジヨード（１，５‐シクロオクタジエン）プラチニウム（ＩＩ）（［ＰｔＩ２（ｃｏｄ）］）２ｇ（３．５９ｍｍｏｌ）と２，６‐ジメチルフェニルイソシアニド１．１６ｇ（７．９０ｍｍｏｌ）とを入れ、そこへ、ＴＨＦ５０ｍｌを加えた後、室温下で４時間攪拌した。その後、反応液をろ過し、濾液を濃縮して析出物を得た。析出物をｎ‐ヘキサン１０ｍｌで３回洗浄し、乾燥後、ジクロロメタン（１０ｍｌ）／ｎ‐ヘキサン（７５ｍｌ）で、再結晶させた。黄色結晶が析出し、真空乾燥することで、一般式（化３）で表される白金単核錯体として［ＰｔＩ２（ｘｙｌｙｌＮＣ）２］を２．５２ｇ得た。収率は、９９％であった。図１は、実施例１の工程１で得た白金単核錯体のＸ線結晶構造解析の結果を示す図である。
<Example 1>
(Process 1)
In a 500 ml Schlenk container under an argon atmosphere, 2 g of diiodo (1,5-cyclooctadiene) platinium (II) ([PtI 2 (cod)]) as a platinum mononuclear complex represented by the general formula (Chemical Formula 2) (3.59 mmol) and 1.16 g (7.90 mmol) of 2,6-dimethylphenyl isocyanide were added, and 50 ml of THF was added thereto, followed by stirring at room temperature for 4 hours. Thereafter, the reaction solution was filtered, and the filtrate was concentrated to obtain a precipitate. The precipitate was washed with 10 ml of n-hexane three times, dried and recrystallized with dichloromethane (10 ml) / n-hexane (75 ml). Yellow crystals were precipitated and vacuum-dried to obtain 2.52 g of [PtI 2 (xylylNC) 2 ] as a platinum mononuclear complex represented by the general formula (Formula 3). The yield was 99%. FIG. 1 is a diagram showing the results of X-ray crystal structure analysis of the platinum mononuclear complex obtained in Step 1 of Example 1.
（工程２）
アルゴン雰囲気下で、５００ｍｌのシュレンク容器に［ＰｔＩ２（ｘｙｌｙｌＮＣ）２］２ｇ（２．８１ｍｍｏｌ）とマグネシウム０．６９ｇ（２８．１ｍｍｏｌ）とを入れ、そこへ、ジクロロメタン（１５０ｍｌ）／ＴＨＦ（５０ｍｌ）を加えた後、４０℃で１６時間攪拌した。その後、反応液を濾過し、濾液を濃縮して析出物を得た。析出物をｎ‐ヘキサン１０ｍｌで３回洗浄し、乾燥後、ジクロロメタン（１０ｍｌ）／ｎ‐ヘキサン（７５ｍｌ）で、再結晶させた。黄色結晶が析出し、真空乾燥することで、一般式（化１）で表される白金二核錯体として［Ｐｔ２Ｉ２（ｘｙｌｙｌＮＣ）４］を１．４８ｇ得た。収率は、９０％であった。図２は、実施例１の工程２で得た白金二核錯体のＸ線結晶構造解析の結果を示す図である。
(Process 2)
Under an argon atmosphere, 2 g (2.81 mmol) of [PtI 2 (xylylNC) 2 ] and 0.69 g (28.1 mmol) of magnesium were put into a 500 ml Schlenk container, and dichloromethane (150 ml) / THF (50 ml) was added thereto. And then stirred at 40 ° C. for 16 hours. Thereafter, the reaction solution was filtered, and the filtrate was concentrated to obtain a precipitate. The precipitate was washed with 10 ml of n-hexane three times, dried and recrystallized with dichloromethane (10 ml) / n-hexane (75 ml). Yellow crystals were precipitated and vacuum-dried to obtain 1.48 g of [Pt 2 I 2 (xylylNC) 4 ] as a platinum binuclear complex represented by the general formula (Chemical Formula 1). The yield was 90%. 2 is a diagram showing the results of X-ray crystal structure analysis of the platinum binuclear complex obtained in Step 2 of Example 1. FIG.
実施例１の工程１で得られた［ＰｔＩ２（ｘｙｌｙｌＮＣ）２］及び実施例１の工程２で得られた［Ｐｔ２Ｉ２（ｘｙｌｙｌＮＣ）４］のＩＲ及び１Ｈ ＮＭＲデータを表１に、１３Ｃ ＮＭＲデータを表２に、元素分析データを表３に示す。 Table 1 shows the IR and 1 H NMR data of [PtI 2 (xylylNC) 2 ] obtained in Step 1 of Example 1 and [Pt 2 I 2 (xylylNC) 4 ] obtained in Step 2 of Example 1. 13 C NMR data are shown in Table 2, and elemental analysis data are shown in Table 3.
本発明に係る白金二核錯体は、均一系白金錯体触媒として利用できる。また、本発明に係る白金二核錯体は、白金ナノ粒子担持触媒の前駆体として利用でき、白金ナノ粒子担持触媒の前駆体は、排ガス浄化触媒として利用できる。 The platinum binuclear complex according to the present invention can be used as a homogeneous platinum complex catalyst. The platinum binuclear complex according to the present invention can be used as a precursor of a platinum nanoparticle-supported catalyst, and the precursor of the platinum nanoparticle-supported catalyst can be used as an exhaust gas purification catalyst.
Claims (5)
（化１）［Ｐｔ２Ｘ２Ｌ１ ４］
一般式（化１）において、Ｘはハロゲン原子、Ｌ１は構成元素として炭素、水素及び窒素からなる中性配位子を示す。 A platinum binuclear complex represented by the general formula (Chemical Formula 1) and having a bond between platinum (I) and platinum (I).
(Chemical formula 1) [Pt 2 X 2 L 1 4 ]
In the general formula (Formula 1), X represents a halogen atom, and L 1 represents a neutral ligand composed of carbon, hydrogen and nitrogen as constituent elements.
一般式（化３）で表される白金単核錯体を、ハロゲン引き抜き能を有するＰｔ（ＩＩ）からＰｔ（Ｉ）への１電子還元剤を用いて還元し、一般式（化１）で表される白金二核錯体を得る工程２とを有することを特徴とする白金二核錯体の製造方法。
（化２）［ＰｔＸ２Ｌ２］
一般式（化２）において、Ｘはハロゲン原子、Ｌ２は中性配位子を示す。
（化３）［ＰｔＸ２Ｌ１ ２］
一般式（化３）において、Ｘはハロゲン原子、Ｌ１は構成元素として炭素、水素及び窒素からなる中性配位子を示す。 A platinum mononuclear complex represented by the general formula (Chemical Formula 2) is reacted with a neutral ligand L 1 composed of carbon, hydrogen and nitrogen as constituent elements to form a platinum single molecule represented by the general formula (Chemical Formula 3). Step 1 for obtaining a nuclear complex;
The platinum mononuclear complex represented by the general formula (Chemical Formula 3) is reduced using a one-electron reducing agent from Pt (II) to Pt (I) having halogen abstraction ability, and represented by the general formula (Chemical Formula 1). And a step 2 of obtaining a platinum binuclear complex to be produced.
(Chemical Formula 2) [PtX 2 L 2 ]
In the general formula (Formula 2), X represents a halogen atom, and L 2 represents a neutral ligand.
(Chemical formula 3) [PtX 2 L 1 2 ]
In the general formula (Formula 3), X represents a halogen atom, and L 1 represents a neutral ligand composed of carbon, hydrogen and nitrogen as constituent elements.
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