JPH0615554B2 - New dihydrido rhodium complex - Google Patents
New dihydrido rhodium complexInfo
- Publication number
- JPH0615554B2 JPH0615554B2 JP62097512A JP9751287A JPH0615554B2 JP H0615554 B2 JPH0615554 B2 JP H0615554B2 JP 62097512 A JP62097512 A JP 62097512A JP 9751287 A JP9751287 A JP 9751287A JP H0615554 B2 JPH0615554 B2 JP H0615554B2
- Authority
- JP
- Japan
- Prior art keywords
- dihydrido
- rhodium
- rhodium complex
- present
- new
- 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 - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は下記の式（Ｉ）で示されるジヒドリド（１，３
−ジフェニルトリアゼニド）〔ビス（１，２−ジフェニ
ルホスフィノ）ベンゼン〕ロジウム(III)に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a dihydride (1,3) represented by the following formula (I):
-Diphenyltriazenide) [bis (1,2-diphenylphosphino) benzene] rhodium (III).
式： （式中のphはフェニル基を表わす） 〔従来の技術〕 本発明のジヒドリド（１，３−ジフェニルトリアゼニ
ド）〔ビス（１，２−ジフェニルホスフィノ）ベンゼ
ン〕ロジウム(III)（以下ジヒドリドロジウム錯体と略
記する）は文献末記載の新規化合物である。formula: (Ph in the formula represents a phenyl group) [Prior Art] Dihydrido (1,3-diphenyltriazenide) [bis (1,2-diphenylphosphino) benzene] rhodium (III) (hereinafter referred to as diphenyl) of the present invention (Abbreviated as hydrido rhodium complex) is a novel compound described at the end of the literature.
本発明者らは以前よりロジウム錯体について種々研究し
てきたが、先に本発明のジヒドリドロジウム錯体と類縁
化合物であるジヒドリド（１，３−ジフェニルトリアゼ
ニド）ビス（トリフェニルホスフィン）ロジウム(III)
が四塩化炭素又はテトラヒドロフランと組み合わせた系
でメタクリル酸メチル（ＭＭＡ）等のビニルモノマーの
重合開始剤になることを見出し報告した（日本化学会誌
1983(8)P1196〜1199；高分子論文集1984(11)P679〜683
等）。The present inventors have variously studied rhodium complexes, and previously, the dihydrido rhodium complex of the present invention and a related compound, dihydrido (1,3-diphenyltriazenide) bis (triphenylphosphine) rhodium (III )
Was found to be a polymerization initiator for vinyl monomers such as methyl methacrylate (MMA) in a system combined with carbon tetrachloride or tetrahydrofuran (Chemical Society of Japan).
1983 (8) P1196-1199; Polymers Collection 1984 (11) P679-683
etc).
本発明の新規なジヒドリドロジウム錯体はこれら一連の
研究の中から生まれたものであって、先に報告した本発
明と類縁のロジウム錯体には見られなかった水素化触媒
としての働きを該錯体が有していることを見出し、本発
明をなした。The novel dihydrido rhodium complex of the present invention was born out of these series of studies, and the complex functions as a hydrogenation catalyst not found in the rhodium complex related to the present invention previously reported. The present invention was made by discovering that
すなわち、本発明は前記した式（Ｉ）で示される新規な
ジヒドリドロジウム錯体、即ちジヒドリド（１，３−ジ
フェニルトリアゼニド）〔ビス（１，２−ジフェニルホ
スフィノ）ベンゼン〕ロジウム(III)を提供するもので
ある。That is, the present invention relates to a novel dihydrido rhodium complex represented by the above formula (I), that is, dihydrido (1,3-diphenyltriazenide) [bis (1,2-diphenylphosphino) benzene] rhodium (III) Is provided.
本発明のジヒドリドロジウム錯体は、次に示す方法で製
造することができる。The dihydrido rhodium complex of the present invention can be produced by the following method.
塩化ロジウム溶液に１，３−ジフェニルトリアゼン及び
苛性カリ溶液を加温、攪拌下に加え、反応せしめる。次
にこの反応液を煮沸させたトルフェニルホスフィン溶液
中に滴下し、さらに反応を進めた後、自然冷却する。生
成した沈殿物をろ別し、溶媒及び水で逐次洗浄した後、
乾燥すると目的とするジヒドリドロジウム錯体が得られ
る。1,3-Diphenyltriazene and a caustic potash solution are added to the rhodium chloride solution under heating and stirring to react. Next, this reaction solution is dropped into a boiled triphenylphosphine solution, the reaction is further advanced, and then naturally cooled. The precipitate formed was filtered off, washed successively with the solvent and water,
When dried, the desired dihydrido rhodium complex is obtained.
なお、溶媒はアルコール類、特にエタノールが好まし
い。The solvent is preferably alcohols, especially ethanol.
このようにして製造されたジヒドリドロジウム錯体は融
点140〜148℃の黒色又は黒褐色粉末であり、実施例で具
体的に示すように元素分析及び赤外吸収スペクトル（Ｉ
Ｒ）及び核磁気共鳴スペクトル（ＮＭＲ）の測定により
確認（同定）することができる。The dihydrido rhodium complex thus produced is a black or blackish brown powder having a melting point of 140 to 148 ° C., and elemental analysis and infrared absorption spectrum (I
R) and nuclear magnetic resonance spectrum (NMR) can be confirmed (identified).
本発明のジヒドリドロジウム錯体はＭＭＡ，α−オレフ
ィン等の重合開始剤となるほか、常温常圧という温和な
条件で水素化を進めることができる優れた水素化触媒と
して有用なものである。したがって、従来水素化の難し
かった種々の官能基を持った化合物、或いは熱に不安定
なアミノ酸化合物等の水素化に貢献するものと期待され
る。INDUSTRIAL APPLICABILITY The dihydrido rhodium complex of the present invention serves as a polymerization initiator for MMA, α-olefin and the like, and is useful as an excellent hydrogenation catalyst capable of promoting hydrogenation under mild conditions such as normal temperature and normal pressure. Therefore, it is expected to contribute to the hydrogenation of compounds having various functional groups, which have been difficult to hydrogenate conventionally, or amino acid compounds that are unstable to heat.
以下、実施例、参考例をあげて本発明を具体的に説明す
るが、本発明はこれらによって限定されるものではな
い。Hereinafter, the present invention will be specifically described with reference to Examples and Reference Examples, but the present invention is not limited thereto.
実施例１ あらかじめ200mlの三つ口フラスコ中に窒素雰囲気下、
トリフェニルホスフィン（ＰＰｈ３）1.62ｇをエタノー
ル30mlに溶解せしめた溶液を入れ、煮沸させておく。Example 1 In a 200 ml three-necked flask in advance under a nitrogen atmosphere,
A solution prepared by dissolving 1.62 g of triphenylphosphine (PPh 3 ) in 30 ml of ethanol is added and boiled.
（注：ph＝フェニル基、以下同じ） 別に、塩化ロジウム（ＲｈＣｌ３・３Ｈ２Ｏ）0.39ｇを
エタノール30mlに溶解し、約50℃に加温する。(Note: ph = phenyl, the same applies hereinafter) separately, rhodium chloride (RhCl 3 · 3H 2 O) 0.39g was dissolved in ethanol 30 ml, warmed to about 50 ° C..
対いでこの塩化ロジウム溶液中に攪拌しながら１，３−
ジフェニルトリアゼン（ＰｈＮＨＮ＝ＮＰｈ）0.6ｇを
エタノール15mlに溶解した溶液、及び苛性カリ（ＫＯ
Ｈ）0.6ｇをエタノール15mlに溶解した溶液を添加し、
約５分間攪拌下に反応をさせる。In contrast, while stirring in this rhodium chloride solution 1,3-
A solution of 0.6 g of diphenyltriazene (PhNHN = NPh) in 15 ml of ethanol and caustic potash (KO)
H) Add a solution of 0.6 g dissolved in 15 ml of ethanol,
The reaction is allowed to proceed for about 5 minutes with stirring.
生成した混合反応液を先に調整、煮沸してある前記のト
リフェニルホスフィン溶液に滴下する。The mixed reaction solution thus produced is first added to the previously prepared and boiled triphenylphosphine solution.
滴下後約30分間煮沸下におき、反応を進めた後、自然冷
却する。After dropping, leave it under boiling for about 30 minutes to allow the reaction to proceed, and then allow to cool naturally.
生成した沈殿物をろ別し、エタノール、水、メタノール
の順で洗浄し、減圧乾燥を行うとmp140〜148℃の黒色粉
末が収量0.45〜0.50ｇ、収率（ＲｈＣｌ３・３Ｈ２Ｏ換
算）40〜45％で得られた。The resulting precipitate was filtered off, ethanol, water, sequentially washed with methanol, drying under reduced pressure the Mp140～148 ° C. black powder Yield 0.45～0.50G, yield (RhCl 3 · 3H 2 O equivalent) Obtained in 40-45%.
該粉末を元素分析（注１）したところ 理論値(%) Ｃ，67.48：Ｈ，4.85Ｎ，5.62：Rh13.76 分析値(%) Ｃ，67.40：Ｈ，4.95Ｎ，5.23：Rh13.11 の結果を得た。The powder was subjected to elemental analysis (Note 1): theoretical value (%) C, 67.48: H, 4.85 N, 5.62: Rh13.76 Analytical value (%) C, 67.40: H, 4.95 N, 5.23: Rh13.11 I got the result.
又、日本分光(株)製ＩＲ−Ｇを用い流動パラフィン法に
て赤外吸収スペクトル（ＩＲ）の測定を行ったところ次
の結果を得た。 Further, the infrared absorption spectrum (IR) was measured by the liquid paraffin method using IR-G manufactured by JASCO Corporation, and the following results were obtained.
・1272,1588(cm-1) 〔トリアゼニド錯体配位子由来の吸収〕 ・2032,2056,2080(cm-1) 〔Ｒｈ−Ｈ由来の吸収〕 ・760cm-1＜肩の吸収＞ 〔オルト置換ベンゼン由来の吸収〕 更に、日本電子(株)製JNM-FX100(FTNMR)100メガヘルツ
を用い常温、クロロホルム−ｄ溶媒にて、１ＨＮＭＲの
測定をしたところδ＝約−17.8を得た（１ＪRh-H＝約17
HZ，２ＪP-H＝約16HZ）。-1272,1588 (cm -1 ) [absorption derived from triazenide complex ligand] -2032,2056,2080 (cm -1 ) [absorption derived from Rh-H] -760 cm -1 <shoulder absorption] [ortho substitution absorption attributable benzene] Furthermore, JEOL Ltd. JNM-FX100 (FTNMR) room temperature using a 100 megahertz, with chloroform -d solvent, 1 was measured HNMR [delta] = about -17.8 was obtained (1 J Rh-H = approx. 17
HZ, 2 J PH = about 16HZ).
以上の結果から目的とするジヒドリド（１，３−ジフェ
ニルトリアゼニド）〔ビス（１，２−ジフェニルホスフ
ィノ）ベンゼン〕ロジウム(III)であることが確認され
た。From the above results, it was confirmed that the target compound was dihydrido (1,3-diphenyltriazenide) [bis (1,2-diphenylphosphino) benzene] rhodium (III).
参考例１〔本発明ジヒドリドロジウム錯体による桂皮酸
の水素化〕 表−１に示す各種溶媒20ml中に桂皮酸１×10-3モル及び
本発明のジヒドリドロジウム錯体１×10-4モルを加え30
℃で２時間、常圧、水素存在下に桂皮酸の水素化反応を
行った。結果を表−１に示す。Reference Example 1 [Hydrogenation of cinnamic acid by the dihydrido rhodium complex of the present invention] In 20 ml of each solvent shown in Table 1, 1 × 10 -3 mol of cinnamic acid and 1 × 10 -4 mol of the dihydrido rhodium complex of the present invention were added. Plus 30
The hydrogenation reaction of cinnamic acid was carried out in the presence of hydrogen at atmospheric pressure for 2 hours. The results are shown in Table-1.
表−１から明らかな通りＤＭＳＯ溶媒を用いたとき桂皮
酸の水素化物であるデヒドロ桂皮酸が100％の収率で得
られている。As is clear from Table 1, dehydrocinnamic acid, which is a hydride of cinnamic acid, was obtained with a DMSO solvent in a yield of 100%.
比較のため公知のジヒドリド（１，３−ジフェニルトリ
アゼニド）〔ビス（トリフェニルホスフィン）ロジウム
(III)を用いＤＭＳＯ溶媒で上記と同一条件下に桂皮酸
の水素化反応を行ったところ収率は10％にすぎなかっ
た。For comparison, known dihydride (1,3-diphenyltriazenide) [bis (triphenylphosphine) rhodium
The hydrogenation reaction of cinnamic acid was carried out using (III) in a DMSO solvent under the same conditions as above, and the yield was only 10%.
参考例２〔本発明ジヒドリドロジウム錯体によるＭＭＡ
の重合〕 表−２に示す各溶媒５ml中にメタクリル酸メチル（ＭＭ
Ａ）５ml、ならびに本発明ジヒドリドロジウム錯体2.0
×10-3モル／、四塩化炭素（ＣＣｌ４）1.0×10-3モ
ル／加え、反応器内を窒素置換した後、50℃で30分
間、ＭＭＡを重合せしめた。結果を表−２に示す。 Reference Example 2 [MMA by the dihydrido rhodium complex of the present invention
Polymerization of Methyl Methacrylate (MM
A) 5 ml, and dihydrido rhodium complex 2.0 of the present invention
× 10 -3 mol /, carbon tetrachloride (CCl 4 ) 1.0 × 10 -3 mol / added, the inside of the reactor was replaced with nitrogen, and MMA was polymerized at 50 ° C for 30 minutes. The results are shown in Table-2.
なお、生成したＰＭＭＡの平均分子量（）はベンゼン
溶液、30℃における極限粘度〔η〕から、次式により算
出した。 The average molecular weight () of the produced PMMA was calculated from the intrinsic viscosity [η] at 30 ° C. in a benzene solution by the following formula.
〔η〕＝5.2×10-50.76[Η] = 5.2 × 10 -5 0.76
Claims (1)
ド）〔ビス（１，２−ジフェニルホスフィノ）ベンゼ
ン〕ロジウム(III)。1. Formula (I) (In the formula, ph represents a phenyl group), dihydrido (1,3-diphenyltriazenide) [bis (1,2-diphenylphosphino) benzene] rhodium (III).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62097512A JPH0615554B2 (en) | 1987-04-22 | 1987-04-22 | New dihydrido rhodium complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62097512A JPH0615554B2 (en) | 1987-04-22 | 1987-04-22 | New dihydrido rhodium complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63307889A JPS63307889A (en) | 1988-12-15 |
| JPH0615554B2 true JPH0615554B2 (en) | 1994-03-02 |
Family
ID=14194311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62097512A Expired - Lifetime JPH0615554B2 (en) | 1987-04-22 | 1987-04-22 | New dihydrido rhodium complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0615554B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4242469A1 (en) * | 1992-12-16 | 1994-06-23 | Wacker Chemie Gmbh | Catalysts for hydrosilylation reactions |
| DE4324685A1 (en) * | 1993-07-22 | 1995-01-26 | Wacker Chemie Gmbh | Organosiloxane-bound transition metal complexes |
| US5548070A (en) * | 1993-07-22 | 1996-08-20 | Wacker-Chemie Gmbh | Organosilicon compounds having triazene groups |
| GB0300821D0 (en) * | 2003-01-14 | 2003-02-12 | Bp Chem Int Ltd | Polymerisation catalysts |
-
1987
- 1987-04-22 JP JP62097512A patent/JPH0615554B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63307889A (en) | 1988-12-15 |
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