JPH10259206A - Samarium complex - Google Patents
Samarium complexInfo
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- JPH10259206A JPH10259206A JP6761197A JP6761197A JPH10259206A JP H10259206 A JPH10259206 A JP H10259206A JP 6761197 A JP6761197 A JP 6761197A JP 6761197 A JP6761197 A JP 6761197A JP H10259206 A JPH10259206 A JP H10259206A
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- tert
- thf
- oar
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規な二価サマリ
ウム錯体及びその用途に関するものである。[0001] The present invention relates to a novel divalent samarium complex and its use.
【０００２】[0002]
【従来の技術】二価ランタノイドである二価サマリウム
(Sm)の錯体については、従来、Cp*-（ペンタメチルシク
ロペンタジエニルアニオン）や I- など同一の配位子を
複数個有する錯体を中心に研究が進められてきた。最
近、新規な配位子を有するランタノイド錯体として、ビ
スアリールオキシドアニオン(ArO- ) を配位子とする二
価ランタノイド錯体(ArO)2Ln (LnはSm又はYbを示し、Ar
O は2,6-ジ-tert-ブチル-4- メチルフェノキシドアニオ
ンを示す) についての特徴ある反応性が報告され、アリ
ールオキシド配位子がランタノイド錯体に対して有用な
配位子であることが明らかにされた(Hou, Z., et al.,
J. Am. Chem. Soc., 117, pp.4421-4422, 1995; Yoshim
ura, T., et al., Organometallics, 14, pp.4858-486
4, 1995; Hou,Z., et al., J. Am. Chem. Soc., 116, p
p.11169-11170, 1994)。しかしながら、異なる配位子を
有するサマリウム錯体は配位子の再配列などによって合
成が困難であり、ほとんど研究されていない。2. Description of the Related Art Divalent samarium which is a divalent lanthanoid
The complex of (Sm), conventionally, Cp * - (pentamethylcyclopentadienyl anion) or I - Studies about the complex having a plurality of identical ligand such as has been promoted. Recently, as a lanthanoid complex having a novel ligand, a divalent lanthanoid complex (ArO) 2 Ln having a bisaryloxide anion (ArO − ) as a ligand (Ln represents Sm or Yb,
O represents 2,6-di-tert-butyl-4-methylphenoxide anion), indicating that aryl oxide ligands are useful ligands for lanthanoid complexes. (Hou, Z., et al.,
J. Am. Chem. Soc., 117, pp.4421-4422, 1995; Yoshim
ura, T., et al., Organometallics, 14, pp.4858-486
4, 1995; Hou, Z., et al., J. Am. Chem. Soc., 116, p.
p.11169-11170, 1994). However, samarium complexes having different ligands are difficult to synthesize due to ligand rearrangement and the like, and are hardly studied.
【０００３】例えば、二価サマリウムアミド錯体Sm[N(S
iMe3)2]2(THF)2（Me: メチル基；THF:テトラヒドロフラ
ン配位子）を二当量の2,6-ジ-tert-ブチル-4- メチルフ
ェノールなどのヒドロキシアリール化合物と反応させる
と、対応する二価サマリウムアリールオキシド錯体 (Ar
O)2Sm(THF)3 が得られること、並びに、この錯体をI2と
反応させるとアリールオキシド配位子を有する三価のサ
マリウム・ヨウ化物:(ArO)2Sm(THF)2I が得られること
が知られている（日本化学会平成７年春季年会, 演題番
号3H5/43, 京都市）。For example, a divalent samarium amide complex Sm [N (S
iMe 3 ) 2 ] 2 (THF) 2 (Me: methyl group; THF: tetrahydrofuran ligand) is reacted with two equivalents of a hydroxyaryl compound such as 2,6-di-tert-butyl-4-methylphenol. , The corresponding divalent samarium aryl oxide complex (Ar
O) 2 Sm (THF) 3 is obtained, and when this complex is reacted with I 2 , trivalent samarium iodide having an aryl oxide ligand: (ArO) 2 Sm (THF) 2 I It is known that it can be obtained (Chemical Society of Japan 1995 Spring Meeting, Abstract No. 3H5 / 43, Kyoto City).
【０００４】また、最近、 [Cp* Sm(OAr1)Cp* K(THF)2]
n（式中、Cp* はペンタメチルシクロペンタジエニル配
位子を示し、 Ar1O は2,6-ジ-tert-ブチル-4- メチルフ
ェノキシド配位子を示し、THF はテトラヒドロフラン配
位子を示し、n は該錯体が [Cp* Sm(OAr1)Cp* K(THF)2]
を繰り返し単位とするポリメリック錯体であることを示
す）で表される二価のサマリウム錯体が提案されている
(日本化学会第70春季年会、演題番号 2B114、1996年３
月29日；希土類 No.28、日本希土類学会発行、1996年５
月16日）。Recently, [Cp * Sm (OAr 1 ) Cp * K (THF) 2 ]
n (where Cp * represents a pentamethylcyclopentadienyl ligand, Ar 1 O represents a 2,6-di-tert-butyl-4-methylphenoxide ligand, and THF represents a tetrahydrofuran ligand And n is the complex represented by [Cp * Sm (OAr 1 ) Cp * K (THF) 2 ]
Dimeric samarium complex represented by the following formula:
(The 70th Annual Meeting of the Chemical Society of Japan, Abstract No. 2B114, March 1996
29th; Rare Earth No.28, published by The Japan Rare Earth Society, May 1996
March 16).
【０００５】[0005]
【発明が解決しようとする課題及び課題を解決するため
の手段】本発明は、例えば、重合反応などの種々の有機
合成反応や、上記の二価サマリウム錯体の製造のための
原料物質として有用な二価サマリウム錯体を提供するこ
とを課題としている。本発明者らは上記の課題を解決す
べく鋭意努力した結果、(Cp* )2Sm(THF)2（式中、Cp*
はペンタメチルシクロペンタジエニル配位子を示し、TH
F はテトラヒドロフラン配位子を示す) で表されるサマ
リウム錯体を2,6-ジ-tert-ブチル-4- メチルフェノール
などと反応させることにより、 [Cp* Sm(OAr)]2 で表さ
れる新規な二価サマリウム錯体が得られることを見いだ
した (ArOはアリールオキシド配位子を示す）。また、
本発明者らは、この新規サマリウム錯体がエチレン及び
スチレンの重合用触媒として有用であり、Cp* Sm(OAr)
(HMPA)2や [Cp* Sm(OAr) Cp* K(THF)2]n などの有用な
サマリウム錯体の製造原料としても利用できることを見
いだした。本発明はこれらの知見を基にして完成された
ものである。DISCLOSURE OF THE INVENTION The present invention is useful as a raw material for various organic synthesis reactions such as a polymerization reaction and for producing the above-mentioned divalent samarium complex. It is an object to provide a divalent samarium complex. The present inventors have made intensive efforts to solve the above problems, and as a result, (Cp * ) 2 Sm (THF) 2 (where Cp *
Represents a pentamethylcyclopentadienyl ligand, and TH
F represents a tetrahydrofuran ligand), and is reacted with 2,6-di-tert-butyl-4-methylphenol to form [Cp * Sm (OAr)] 2 A new divalent samarium complex was found to be obtained (ArO indicates an aryloxide ligand). Also,
The present inventors have found that this novel samarium complex is useful as a catalyst for the polymerization of ethylene and styrene, and Cp * Sm (OAr)
It has been found that it can be used as a raw material for producing useful samarium complexes such as (HMPA) 2 and [Cp * Sm (OAr) Cp * K (THF) 2 ] n . The present invention has been completed based on these findings.
【０００６】すなわち本発明は、式： [Cp* Sm(OAr)]2
（式中、Cp* はペンタメチルシクロペンタジエニル配位
子を示し、ArO はアリールオキシド配位子を示す）で表
されるサマリウム錯体を提供するものである。この発明
の好ましい態様によれば、アリールオキシド配位子が2,
6-ジ-tert-ブチル-4- メチルフェノキシド配位子、2,6-
ジ-tert-ブチルフェノキシド配位子、又は2,4,6-トリ-t
ert-ブチルフェノキシド配位子である上記錯体が提供さ
れる。また、本発明の別の態様によれば、 (Cp* )2Sm(T
HF)2（式中、Cp* はペンタメチルシクロペンタジエニル
配位子を示し、THF はテトラヒドロフラン配位子を示
す) で表されるサマリウム錯体をヒドロキシアリール化
合物と反応させる工程を含む、上記サマリウム錯体の製
造方法；スチレン及びエチレンの共重合用触媒である上
記サマリウム錯体；並びに、上記サマリウム錯体の存在
下でスチレン及びエチレンの共重合を行う方法が提供さ
れる。That is, the present invention provides a compound represented by the formula: [Cp * Sm (OAr)] 2
(Wherein Cp * represents a pentamethylcyclopentadienyl ligand, and ArO represents an aryloxide ligand). According to a preferred embodiment of the present invention, the aryl oxide ligand is 2,2.
6-di-tert-butyl-4-methylphenoxide ligand, 2,6-
Di-tert-butylphenoxide ligand, or 2,4,6-tri-t
Provided is the above complex, which is an ert-butylphenoxide ligand. According to another aspect of the present invention, (Cp * ) 2 Sm (T
HF) 2 (wherein Cp * represents a pentamethylcyclopentadienyl ligand and THF represents a tetrahydrofuran ligand), the samarium complex comprising reacting the samarium complex with a hydroxyaryl compound. A method for producing a complex; a samarium complex as a catalyst for copolymerizing styrene and ethylene; and a method for copolymerizing styrene and ethylene in the presence of the samarium complex.
【０００７】[0007]
【発明の実施の形態】本発明のサマリウム錯体は下記の
式： [Cp* Sm(OAr)]2 で表されることを特徴としてい
る。式中、Cp* はペンタメチルシクロペンタジエニル配
位子を示し、ArO はアリールオキシド配位子を示す。ア
リールオキシド配位子としては、好ましくは置換フェノ
キシドアニオンを用いることができ、置換フェノキシド
アニオンとしては、例えば、ベンゼン環上に１個又は２
個以上、好ましくは２個又は３個のアルキル基が置換し
たものを用いることができる。ベンゼン環上に２個又は
３個のアルキル基を有する場合、これらのアルキル基は
同一でも異なっていてもよく、これらのアルキル基のう
ちの２個がそれぞれベンゼン環上の2-位及び6-位（フェ
ノキシドのベンゼン環においてオキシド基が置換した炭
素原子を1-位とする）に置換して、2,6-ジアルキル置換
フェノキシドアニオンを形成していることが好ましい。
３個のアルキル基を有する場合には、ベンゼン環上の2-
位、4-位、及び6-位に置換していることが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The samarium complex of the present invention is characterized by being represented by the following formula: [Cp * Sm (OAr)] 2 . In the formula, Cp * represents a pentamethylcyclopentadienyl ligand, and ArO represents an aryloxide ligand. As the aryl oxide ligand, a substituted phenoxide anion can be preferably used. As the substituted phenoxide anion, for example, one or two on the benzene ring can be used.
One or more, preferably two or three alkyl groups are substituted. When there are two or three alkyl groups on the benzene ring, these alkyl groups may be the same or different, and two of these alkyl groups are 2- and 6-positions on the benzene ring, respectively. It is preferable to form a 2,6-dialkyl-substituted phenoxide anion by substituting at the 1-position (the carbon atom substituted by the oxide group in the benzene ring of the phenoxide is 1-position).
In the case of having three alkyl groups, 2-alkyl on the benzene ring
Substitution at the 4-, 6-, and 6-positions is preferred.
【０００８】ベンゼン環上の2-位、6-位に置換するアル
キル基としては、錯体の安定性などの観点から、イソプ
ロピル基、tert- ブチル基、ネオペンチル基などの立体
的に嵩高いC3-C6 アルキル基を用いることが好適であ
る。例えば、2,6-ジ-tert-ブチルフェノキシドアニオ
ン、2,6-ジイソプロピルフェノキシドアニオン、2,6-ジ
ネオペンチルフェノキシドアニオン、2-tert- ブチル-6
- イソプロピルフェノキシドアニオン、2-tert- ブチル
-6- ネオペンチルフェノキシドアニオン、又は2-イソプ
ロピル-6- ネオペンチルフェノキシドアニオンなどを用
いることができる。これらのうち、2,6-ジ-tert-ブチル
フェノキシドアニオンを特に好適に用いることができ
る。The alkyl group substituted at the 2- or 6-position on the benzene ring is preferably a sterically bulky C 3 group such as an isopropyl group, a tert-butyl group or a neopentyl group from the viewpoint of the stability of the complex. it is preferred to use -C 6 alkyl group. For example, 2,6-di-tert-butylphenoxide anion, 2,6-diisopropylphenoxide anion, 2,6-dineopentylphenoxide anion, 2-tert-butyl-6
-Isopropylphenoxide anion, 2-tert-butyl
-6-neopentylphenoxide anion or 2-isopropyl-6-neopentylphenoxide anion can be used. Among them, 2,6-di-tert-butylphenoxide anion can be particularly preferably used.
【０００９】また、これらの2,6-ジアルキル置換フェノ
キシドアニオンのベンゼン環がさらに１個又は２個以
上、好ましくは１個のアルキル基を有する場合、そのよ
うなアルキル基としてはC1-C4 アルキル基が好適であ
り、該アルキル基の置換位置としては4-位が好適であ
る。例えば、2,6-ジアルキル置換フェノキシドアニオン
のベンゼン環の4-位にメチル基、エチル基、イソプロピ
ル基、tert- ブチル基などのC1-C4 アルキル基が導入さ
れたフェノキシドアニオンを配位子として有する錯体
は、溶解性などの観点から好ましい。より具体的には、
配位子として2,6-ジ-tert-ブチル-4- メチルフェノキシ
ドアニオン又は2,4,6-トリ-tert-ブチルフェノキシドア
ニオンを有する錯体は本発明の方法に特に好適に使用で
きる。When the benzene ring of these 2,6-dialkyl-substituted phenoxide anions further has one or more, preferably one, alkyl group, the alkyl group may be C 1 -C 4 An alkyl group is preferable, and the substitution position of the alkyl group is preferably the 4-position. For example, a phenoxide anion in which a C 1 -C 4 alkyl group such as a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group is introduced at the 4-position of the benzene ring of a 2,6-dialkyl-substituted phenoxide anion is used as a ligand. Is preferred from the viewpoint of solubility and the like. More specifically,
A complex having 2,6-di-tert-butyl-4-methylphenoxide anion or 2,4,6-tri-tert-butylphenoxide anion as a ligand can be particularly preferably used in the method of the present invention.
【００１０】本発明の錯体は、公知の二価サマリウム錯
体 (Cp* )2Sm(THF)2（式中、Cp* 及びTHF は上記のとお
りである）を当量のヒドロキシアリール化合物 (ArOH)
と反応させることにより収率よく製造することができ
る。原料として用いる (Cp* )2Sm(THF)2は、例えば、公
知の方法（例えば、Evans, W.J., et al., J. Am. Che
m. Soc., 107, 941, 1985などに記載の方法) に従って
容易に入手することができる。m[N(SiMe3)2]2(THF)
2 （SiMe3:トリメチルシリル基）に二当量のヒドロキシ
アリール化合物を反応させることにより容易に製造する
ことができる。ヒドロキシアリール化合物としては、所
望のアリールオキシド配位子に対応する化合物を用いれ
ばよく、例えば、2,6-ジ-tert-ブチル-4- メチルフェノ
キシドアニオンを配位子として導入する場合には、ヒド
ロキシアリール化合物として2,6-ジ-tert-ブチル-4- メ
チルフェノールを用いればよい。The complex of the present invention comprises a known divalent samarium complex (Cp * ) 2 Sm (THF) 2 (where Cp * and THF are as defined above) in an equivalent amount of a hydroxyaryl compound (ArOH).
And can be produced in good yield. (Cp * ) 2 Sm (THF) 2 used as a raw material can be produced, for example, by a known method (eg, Evans, WJ, et al., J. Am. Che.
m. Soc., 107, 941, 1985, etc.). m [N (SiMe 3 ) 2 ] 2 (THF)
2 (SiMe 3 : trimethylsilyl group) can be easily produced by reacting two equivalents of a hydroxyaryl compound. As the hydroxyaryl compound, a compound corresponding to a desired aryl oxide ligand may be used.For example, when introducing 2,6-di-tert-butyl-4-methylphenoxide anion as a ligand, 2,6-Di-tert-butyl-4-methylphenol may be used as the hydroxyaryl compound.
【００１１】本発明の錯体は各種の有機反応の触媒、例
えば、エチレンとスチレンの共重合のための触媒として
用いることができるほか、アリールオキシド配位子を有
する他の有用な二価サマリウム錯体の製造用原料として
用いることもできる。例えば、本発明の錯体をCp*-K
（ペンタメチルシクロペンタジエニドカリウム）と反応
させることにより [Cp* Sm(OAr) Cp* K(THF)2]n で表さ
れるサマリウム錯体を製造することができ、HMPA (ヘキ
サメチルホスホルアミド）と反応させることによりCp*
Sm(OAr)(HMPA)2で表されるサマリウム錯体を製造するこ
とができる。The complex of the present invention can be used as a catalyst for various organic reactions, for example, a catalyst for copolymerization of ethylene and styrene, and a useful divalent samarium complex having an aryloxide ligand. It can also be used as a raw material for production. For example, the complex of the present invention is converted to Cp * -K
(Potassium pentamethylcyclopentadienide) to produce a samarium complex represented by [Cp * Sm (OAr) Cp * K (THF) 2 ] n. ) To react with Cp *
A samarium complex represented by Sm (OAr) (HMPA) 2 can be produced.
【００１２】[0012]
【実施例】以下、本発明を実施例によりさらに具体的に
説明するが、本発明の範囲はこれらの実施例に限定され
ることはない。 例１： [Cp* Sm(OAr)]2 (Ar=2,6-di-tert-Bu-C6H3) (1
a)の製造 (Cp* )2Sm(THF)2 (1.13 g, 2 mmol) の紫色トルエン溶
液 (5 ml) に ArOH (0.41 g, 2 mmol)のトルエン溶液
(5 ml) を加えた。得られた緑色混合液を室温で３時間
攪拌した。溶媒を留去して緑色の結晶生成物を得、トル
エンで洗浄して 1a (1.88 g, 1.92 mmol, 収率 96%) を
得た。 (Cp* )2Sm(THF)2及び１当量の (ArO)2Sm(THF)3
をトルエン中で混合することにより、同様に 1a が 97%
の単離収率で得られた。m.p. 262.5-263.0℃1 H NMR (C6D6, 22℃) δ 33.69 (s, 36 H, tBu), -0.01
(br s, 2 H, para-C6H3), -0.17 (brs, 4H, meta-C
6H3), -5.31 (s, 30H, C5Me5) Anal. Calcd for C48H72O2Sm2: C, 58.72%; H, 7.39%,
Found: C, 58.40%; H, 7.32%EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the scope of the present invention is not limited to these Examples. Example 1: [Cp * Sm (OAr)] 2 (Ar = 2,6-di-tert-Bu-C 6 H 3 ) (1
preparation of a) (Cp *) toluene solution of 2 Sm (THF) 2 (1.13 g, purple toluene solution of 2 mmol) (5 ml) in ArOH (0.41 g, 2 mmol)
(5 ml) was added. The resulting green mixture was stirred at room temperature for 3 hours. The solvent was distilled off to obtain a green crystalline product, which was washed with toluene to obtain 1a (1.88 g, 1.92 mmol, yield 96%). (Cp *) 2 Sm (THF ) 2 and 1 eq (ArO) 2 Sm (THF) 3
Is mixed in toluene, 1a also becomes 97%
Was obtained in an isolated yield. mp 262.5-263.0 ° C 1 H NMR (C 6 D 6 , 22 ° C) δ 33.69 (s, 36 H, tBu), -0.01
(br s, 2 H, para-C 6 H 3 ), -0.17 (brs, 4H, meta-C
6 H 3 ), -5.31 (s, 30H, C 5 Me 5 ) Anal.Calcd for C 48 H 72 O 2 Sm 2 : C, 58.72%; H, 7.39%,
Found: C, 58.40%; H, 7.32%
【００１３】例２： [Cp* Sm(OAr)]2 (Ar=4-Me-2,6-di-
tert-Bu-C6H2) (1b)の製造 例１と同様にして錯体(1b)を95% の収率で得た。m.p. 2
81-282℃1 H NMR (C6D6, 22℃) δ 34.30 (s, 36H, tBu), -0.70
(s, 4 H, C6H2), -4.28(s, 6H, Me), -5.13 (s, 30H, C
5Me5) Anal. Calcd for C50H76O2Sm2: C, 59.46%; H, 7.59%,
Found: C, 59.88%; H, 7.63%Example 2: [Cp * Sm (OAr)] 2 (Ar = 4-Me-2,6-di-
Preparation of tert-Bu-C 6 H 2 ) (1b) Complex (1b) was obtained in a yield of 95% in the same manner as in Example 1. mp 2
81-282 ° C 1 H NMR (C 6 D 6 , 22 ° C) δ 34.30 (s, 36H, tBu), -0.70
(s, 4 H, C 6 H 2 ), -4.28 (s, 6H, Me), -5.13 (s, 30H, C
5 Me 5 ) Anal.Calcd for C 50 H 76 O 2 Sm 2 : C, 59.46%; H, 7.59%,
Found: C, 59.88%; H, 7.63%
【００１４】例３： [Cp* Sm(OAr)]2 (Ar=2,4,6-tri-te
rt-Bu-C6H2) (1c)の製造 例１と同様にして錯体(1c)を96% の収率で得た。U-型チ
ューブに充填した (Cp* )2Sm(THF)2のトルエン溶液中に
ArOH のトルエン溶液をゆっくりと拡散させることによ
り、X 線回折に好適な暗緑色の結晶が得られた。m.p. 2
72.0-272.5℃1 H NMR (C6D6, 22℃) δ 34.40 (s, 36H, ortho-tBu),
-0.27 (s, 4H, C6H2), -3.88 (s, 18H, para-tBu), -5.
10 (s, 30H, C5Me5) Anal. Calcd for C56H88O2Sm2: C, 61.48%; H, 8.11%,
Found: C, 61.33%; H, 8.20% 結晶データー a=b=32.435 (3); c=13.193 (2)Å α= β= 90°; γ= 120 ° fw=1094.12, 三方晶系；空間群：R-3 (No. 148), V =12
019 (3) Å3, Z=9, Dcalcd=1.36 g cm -3 Example 3: [Cp * Sm (OAr)] 2 (Ar = 2,4,6-tri-te
Preparation of rt-Bu-C 6 H 2 ) (1c) Complex (1c) was obtained in a yield of 96% in the same manner as in Example 1. U- was filled in a mold tube (Cp *) 2 Sm (THF ) 2 in toluene solution
Slow diffusion of a toluene solution of ArOH yielded dark green crystals suitable for X-ray diffraction. mp 2
72.0-272.5 ° C 1 H NMR (C 6 D 6 , 22 ° C) δ 34.40 (s, 36H, ortho-tBu),
-0.27 (s, 4H, C 6 H 2 ), -3.88 (s, 18H, para-tBu), -5.
10 (s, 30H, C 5 Me 5 ) Anal.Calcd for C 56 H 88 O 2 Sm 2 : C, 61.48%; H, 8.11%,
Found: C, 61.33%; H, 8.20% Crystallographic data a = b = 32.435 (3); c = 13.193 (2) Å α = β = 90 °; γ = 120 ° fw = 1094.12, trigonal; space group : R-3 (No. 148), V = 12
019 (3) Å 3 , Z = 9, Dcalcd = 1.36 g cm -3
【００１５】例４：Cp* Sm(OAr)(HMPA)2 (Ar=2,6-di-te
rt-Bu-C6H3) (2a)の製造 例１で得た錯体(1a, 98 mg, 0.1 mmol) の THF溶液 (5
ml) にHMPA (70μl, 0.4 mmol)を加えると暗褐色の溶液
が得られた。この溶液を室温で１時間攪拌した後、溶媒
の一部を減圧留去して溶液を濃縮し、エーテルを積層し
て褐色結晶を析出させた (160 mg, 0.188 mmol, 収率94
%)。m.p. 260-262℃. トルエン中で (Cp* )2Sm(THF)2と
ArOHとを反応させ、その反応液中に２当量のHMPAを加え
ることによっても同様に錯体(2a)が得られた。1 H NMR (C6D6, 22℃) δ 5.12 (s, 15H, C5Me5), 4.15
(brs, 36H, NMe), 3.07(t, J=7.7 Hz, 1H, para-C6H3),
2.81 (s, 18H, tBu), 2.51(d, J=7.7 Hz, 2H,meta-C6H
3) Anal. Calcd for C36H72N6O3P2Sm: C, 50.91%; H, 8.54
%; N, 9.89%, Found: C,50.80%; H, 8.41%; N, 10.01%Example 4: Cp * Sm (OAr) (HMPA) 2 (Ar = 2,6-di-te
rt-Bu-C 6 H 3 ) (2a) Preparation of the complex (1a, 98 mg, 0.1 mmol) obtained in Example 1 in THF
HMPA (70 μl, 0.4 mmol) to give a dark brown solution. After the solution was stirred at room temperature for 1 hour, a part of the solvent was distilled off under reduced pressure, the solution was concentrated, and ether was layered to precipitate brown crystals (160 mg, 0.188 mmol, yield 94).
%). mp 260-262 ℃. In toluene with (Cp * ) 2 Sm (THF) 2
The complex (2a) was similarly obtained by reacting with ArOH and adding 2 equivalents of HMPA to the reaction solution. 1 H NMR (C 6 D 6 , 22 ° C) δ 5.12 (s, 15H, C 5 Me 5 ), 4.15
(brs, 36H, NMe), 3.07 (t, J = 7.7 Hz, 1H, para-C 6 H 3 ),
2.81 (s, 18H, tBu), 2.51 (d, J = 7.7 Hz, 2H, meta-C 6 H
3 ) Anal.Calcd for C 36 H 72 N 6 O 3 P 2 Sm: C, 50.91%; H, 8.54
%; N, 9.89%, Found: C, 50.80%; H, 8.41%; N, 10.01%
【００１６】例５：Cp* Sm(OAr)(HMPA)2 (Ar=4-Me-2,6-
di-tert-Bu-C6H2) (2b) の製造 例２で得た錯体(1b)を４当量の HMPA と反応させること
により、例４と同様にして錯体(2b)が92% の収率で得ら
れた。また、トルエン中で (Cp* )2Sm(THF)2とArOHとを
反応させ、その反応液中に２当量の HMPA を加えること
によっても同様に錯体(2b)が得られた。1 H NMR (C6D6, 22℃) δ 5.26 (s, 15H, C5Me5), 4.20
(brs, 36H, NMe), 2.76(s, 18H, tBu), 2.24 (s, 2H, C
6H2), 0.42 (s, 3H, Me).Example 5: Cp * Sm (OAr) (HMPA) 2 (Ar = 4-Me-2,6-
Preparation of di-tert-Bu-C 6 H 2 ) (2b) By reacting the complex (1b) obtained in Example 2 with 4 equivalents of HMPA, the complex (2b) was reduced to 92% in the same manner as in Example 4. Obtained in yield. The complex (2b) was also obtained by reacting (Cp * ) 2 Sm (THF) 2 with ArOH in toluene and adding 2 equivalents of HMPA to the reaction mixture. 1 H NMR (C 6 D 6 , 22 ° C) δ 5.26 (s, 15H, C 5 Me 5 ), 4.20
(brs, 36H, NMe), 2.76 (s, 18H, tBu), 2.24 (s, 2H, C
6 H 2 ), 0.42 (s, 3H, Me).
【００１７】例６：Cp* Sm(OAr)(HMPA)2 (Ar=2,4,6-tri
-tert-Bu-C6H2) (2c) の製造 例３で得た錯体(1c)を４当量の HMPA と反応させること
により、例４と同様にして錯体(2c)が90% の収率で得ら
れた。m.p. 225-227℃. また、トルエン中で (Cp* )2Sm
(THF)2とArOHとを反応させ、その反応液中に２当量の H
MPA を加えることによっても同様に錯体(2c)が得られ
た。1 H NMR (C6D6, 22℃) δ 5.24 (s, 15H, C5Me5), 4.29
(brs, 36H, NMe), 2.73(s, 18H, ortho-tBu), 2.38 (s,
2H, C6H2), -0.44 (s, 9H, para-tBu) Anal. Calcd for C40H80N6O3P2Sm: C, 53.06%; H, 8.91
%; N, 9.28%, Found: C,53.36%; H, 8.84%. N, 9.31%Example 6: Cp * Sm (OAr) (HMPA) 2 (Ar = 2,4,6-tri
Preparation of -tert-Bu-C 6 H 2 ) (2c) By reacting the complex (1c) obtained in Example 3 with 4 equivalents of HMPA, the yield of the complex (2c) was 90% in the same manner as in Example 4. Rate obtained. mp 225-227 ℃. In toluene, (Cp * ) 2 Sm
(THF) 2 is reacted with ArOH, and 2 equivalents of H
Complex (2c) was similarly obtained by adding MPA. 1 H NMR (C 6 D 6 , 22 ° C) δ 5.24 (s, 15H, C 5 Me 5 ), 4.29
(brs, 36H, NMe), 2.73 (s, 18H, ortho-tBu), 2.38 (s,
2H, C 6 H 2 ), -0.44 (s, 9H, para-tBu) Anal.Calcd for C 40 H 80 N 6 O 3 P 2 Sm: C, 53.06%; H, 8.91
%; N, 9.28%, Found: C, 53.36%; H, 8.84%. N, 9.31%
【００１８】例７： [Cp* Sm(OAr) Cp* K(THF)2]n (Ar=
2,6-di-tert-Bu-C6H3)(4a)の製造 例１で得た錯体(1a, 982 mg, 1 mmol)の褐色 THF溶液(1
0 ml) をCp* K (348 mg, 2 mmol)の THF懸濁液 (2 ml)
に加えると直ちに緑色の溶液が得られた。この溶液を室
温で５時間攪拌すると暗緑色の溶液となった。この溶液
を濾過して濾液を減圧濃縮し、トルエンを加えて錯体(4
a)を結晶として得た (1376 mg, 1.70 mmol, 収率85%)。
m.p. 263-264℃ Anal. Calcd for C42H67O3KSm: C, 62.32%; H, 8.34%,
Found: C, 62.39%; H, 8.41%Example 7: [Cp * Sm (OAr) Cp * K (THF) 2 ] n (Ar =
Preparation of 2,6-di-tert-Bu-C 6 H 3 ) (4a) A solution of the complex (1a, 982 mg, 1 mmol) obtained in Example 1 in brown THF (1
0 ml) in Cp * K (348 mg, 2 mmol) in THF (2 ml)
A green solution was obtained immediately upon addition. This solution was stirred at room temperature for 5 hours to form a dark green solution. This solution was filtered, and the filtrate was concentrated under reduced pressure.
a) was obtained as crystals (1376 mg, 1.70 mmol, 85% yield).
mp 263-264 ℃ Anal. Calcd for C 42 H 67 O 3 KSm: C, 62.32%; H, 8.34%,
Found: C, 62.39%; H, 8.41%
【００１９】例８： [Cp* Sm(OAr) Cp* K(THF)2]n (Ar
=4-Me-2,6-di-tert-Bu-C6H2) (4b) 及び [Cp* Sm(OAr)
Cp* K(THF)2]n (Ar=2,4,6-tri-tert-Bu-C6H2) (4c)の製
造 例７と同様にして例２で得た錯体(1b)及び例３で得た錯
体(1c)から、それぞれ錯体(4b)及び錯体(4c)を82% 及び
80% の収率で得た。錯体(4b) m.p. 178-180 ℃ (分解後
に赤色固体となり 300℃までその状態が維持された） Anal. Calcd for C43H69O3KSm: C, 62.72%; H, 8.45%,
Found: C, 63.09%; H, 8.27% 錯体(4c) m.p. 273-274 ℃. Anal. Calcd for C46H75O3KSm: C, 63.83%; H, 8.73%,
Found: C, 63.69%; H, 8.67%Example 8: [Cp * Sm (OAr) Cp * K (THF) 2 ] n (Ar
= 4-Me-2,6-di-tert-Bu-C 6 H 2 ) (4b) and (Cp * Sm (OAr)
Preparation of Cp * K (THF) 2 ] n (Ar = 2,4,6-tri-tert-Bu-C 6 H 2 ) (4c) Complexes (1b) and (1b) obtained in Example 2 in the same manner as in Example 7 From the complex (1c) obtained in Example 3, 82% of the complex (4b) and the complex (4c) were obtained respectively.
Obtained in 80% yield. Complex (4b) mp 178-180 ℃ (Red solid after decomposition and maintained at 300 ℃) Anal. Calcd for C 43 H 69 O 3 KSm: C, 62.72%; H, 8.45%,
Found: C, 63.09%; H, 8.27% complex (4c) mp 273-274 ° C. Anal. Calcd for C 46 H 75 O 3 KSm: C, 63.83%; H, 8.73%,
Found: C, 63.69%; H, 8.67%
【００２０】例９：スチレン及びエチレンの共重合 100 mlのフラスコ中に、例２で得た錯体(1b, 0.1 mmo
l)、トルエン(4 ml)、及びスチレン (6 ml) を加え、常
圧でエチレンを加えて５分間攪拌した後、フラスコを密
閉してさらに12時間攪拌を続けることにより、スチレン
及びエチレンの共重合体が得られた(0.4 g) 。PS/PE=5/
1, Mw=24381, Mw/Mn=2.48.Example 9 Copolymerization of Styrene and Ethylene In a 100 ml flask, the complex obtained in Example 2 (1b, 0.1 mmo
l), toluene (4 ml) and styrene (6 ml) were added, ethylene was added at normal pressure, and the mixture was stirred for 5 minutes. Then, the flask was sealed and stirring was further continued for 12 hours to obtain a copolymer of styrene and ethylene. A polymer was obtained (0.4 g). PS / PE = 5 /
1, Mw = 24381, Mw / Mn = 2.48.
【００２１】[0021]
【発明の効果】本発明のサマリウム錯体はエチレン及び
スチレンの共重合などの有機反応の触媒として利用する
ことができるほか、他の有用な二価サマリウム錯体の製
造用原料として用いることもできる。The samarium complex of the present invention can be used not only as a catalyst for organic reactions such as copolymerization of ethylene and styrene, but also as a raw material for producing other useful divalent samarium complexes.
Claims (4)
ンタメチルシクロペンタジエニル配位子を示し、ArO は
アリールオキシド配位子を示す）で表されるサマリウム
錯体。1. Samarium represented by the formula: [Cp * Sm (OAr)] 2 wherein Cp * represents a pentamethylcyclopentadienyl ligand and ArO represents an aryloxide ligand. Complex.
ブチル-4- メチルフェノキシド配位子、2,6-ジ-tert-ブ
チルフェノキシド配位子、又は2,4,6-トリ-tert-ブチル
フェノキシド配位子である請求項１に記載の錯体。2. The method according to claim 2, wherein the aryl oxide ligand is 2,6-di-tert-
The complex according to claim 1, which is a butyl-4-methylphenoxide ligand, a 2,6-di-tert-butylphenoxide ligand, or a 2,4,6-tri-tert-butylphenoxide ligand.
ある請求項１又は２に記載のサマリム錯体。3. The samarim complex according to claim 1, which is a catalyst for copolymerizing styrene and ethylene.
の存在下でスチレン及びエチレンの共重合を行う方法。4. A method for copolymerizing styrene and ethylene in the presence of the samarium complex according to claim 1 or 2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004003022A1 (en) * | 2002-06-27 | 2004-01-08 | Riken | Catalyst composition |
| WO2006004068A1 (en) * | 2004-07-02 | 2006-01-12 | Riken | Polymerization catalyst compositions containing metallocene complexes and polymers produced by using the same |
-
1997
- 1997-03-21 JP JP06761197A patent/JP3552079B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004003022A1 (en) * | 2002-06-27 | 2004-01-08 | Riken | Catalyst composition |
| WO2006004068A1 (en) * | 2004-07-02 | 2006-01-12 | Riken | Polymerization catalyst compositions containing metallocene complexes and polymers produced by using the same |
| JPWO2006004068A1 (en) * | 2004-07-02 | 2008-05-08 | 独立行政法人理化学研究所 | Polymerization catalyst composition containing metallocene complex and polymer produced using the same |
| US7994267B2 (en) | 2004-07-02 | 2011-08-09 | Riken | Polymerization catalyst compositions containing metallocene complexes and polymers produced by using the same |
| JP5098332B2 (en) * | 2004-07-02 | 2012-12-12 | 独立行政法人理化学研究所 | Polymerization catalyst composition containing metallocene complex and polymer produced using the same |
| US8623976B2 (en) | 2004-07-02 | 2014-01-07 | Riken | Polymerization catalyst compositions containing metallocene complexes and polymers produced by using the same |
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