chloro(cyclopentadienyl)[bis(diphenylphosphino)methane]ruthenium | 71397-33-6

• 物质功能分类: 化学试剂 - 有机试剂 - 烯烃（环状与无环状）
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: chloro(cyclopentadienyl)[bis(diphenylphosphino)methane]ruthenium
• 英文别名: chloro(cyclopentadienyl)[bis(diphenylphosphino)methane]ruthenium(II)；[Cp(dppm)RuCl]；CpRuCl(dppm)；Ru(C5H5)Cl(dppm)；RuCl(dppm)(η-C5H5)；[(η5-C5H5)RuCl(η2-bis(dipehnylphosphino)methane)]；[Ru(η5-C5H5)(κ2-bis(diphenylphosphino)methane)Cl]；(η5-C5H5)Ru(bis(diphenylphosphino)methane)Cl；(η5-C5H5)Ru[eta.2-Ph2PCH2PPh2]；RuCl(dppm)Cp；[(C5H5)RuCl(bis(diphenylphosphino)methane)]；CpRu(bis(diphenylphosphino)methane)Cl；RuCl(bis(diphenylphosphino)methane)Cp；(η5-C5H5)Ru(η2-dppm)Cl；CpRu(dppm)Cl；Chlororuthenium(1+);cyclopenta-1,3-diene;diphenylphosphanylmethyl(diphenyl)phosphane；chlororuthenium(1+);cyclopenta-1,3-diene;diphenylphosphanylmethyl(diphenyl)phosphane
• CAS: 71397-33-6
• 化学式: C₃₀H₂₇ClP₂Ru
• 分子量: 586.015
• InChiKey: BCWUZODDNYQZRM-UHFFFAOYSA-M

物化性质

• 熔点：
  190-196°C
• 稳定性/保质期：
  遵照规定使用和储存，则不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  34
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.03
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• WGK Germany：
  3
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  存储于阴凉干燥处。

SDS

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Section 1: Product Identification
Chemical Name: Chloro(cyclopentadienyl)[bis(diphenylphosphino)methane]ruthenium (II), min. 97%
CAS Registry Number: 71397-33-6
Formula: RuCl(C6H5)[(C6H5)2PCH2P(C6H5)2]
EINECS Number: none
Chemical Family: metal phosphine complex
Synonym: Chloro[bis(diphenylphosphino)methane](cyclopentadienyl)ruthenium (II), min. 97%

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 71397-33-6 100% no data no data

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin, eyes and respiratory tract.
Primary Routes of Exposure: Inhalation, ingestion, skin, eyes
Eye Contact: Causes slight to mild irritation of the eyes.
Skin Contact: Causes mild irritation of the skin.
Inhalation: Irritating to the nose, mucous membranes and respiratory tract.
Ingestion: No information available on the physiological effects of ingestion.
Acute Health Affects: Irritating to skin, eyes and respiratory tract.
Chronic Health Affects: No information on long-term chronic effects.
NTP: No
IARC: No
OSHA: No

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SECTION 4: First Aid Measures
Immediately flush the eyes with copious amounts of water for at least 10-15 minutes. A victim may need
Eye Exposure:
assistance in keeping their eye lids open. Get immediate medical attention.
Wash the affected area with water. Remove contaminated clothes if necessary. Seek medical assistance if
Skin Exposure:
irritation persists.
Remove the victim to fresh air. Closely monitor the victim for signs of respiratory problems, such as difficulty
Inhalation:
in breathing, coughing, wheezing, or pain. In such cases seek immediate medical assistance.
Seek medical attention immediately. Keep the victim calm. Give the victim water (only if conscious). Induce
Ingestion:
vomiting only if directed by medical personnel.

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SECTION 5: Fire Fighting Measures
Flash Point: no data
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: carbon dioxide, dry powder or foam
If this product is involved in a fire, fire fighters should be equipped with a NIOSH approved positive pressure
Special Fire Fighting Procedures:
self-contained breathing apparatus and full protective clothing.
Hazardous Combustion and If involved in a fire, this material may emit irritating fumes.
Decomposion Products:
Unusual Fire or Explosion Hazards: No unusual fire or explosion hazards.

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SECTION 6: Accidental Release Measures
Spill and Leak Procedures: Small spills can be mixed with vermiculite or sodium carbonate and swept up.

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SECTION 7: Handling and Storage
Handling and Storage: Store in a tightly sealed container. Keep in a cool, dry, well ventilated place.

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SECTION 8: Exposure Controls and Personal Protection
Eye Protection: Always wear approved safety glasses when handling a chemical substance in the laboratory.
Skin Protection: Wear protective clothing and gloves.
Ventilation: Handle the material in an efficient fume hood.
If ventilation is not available a respirator should be worn. The use of respirators requires a Respirator
Respirator:
Protection Program to be in compliance with 29 CFR 1910.134.
Ventilation: Handle the material in an efficient fume hood.
Additional Protection: No additional protection required.

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SECTION 9: Physical and Chemical Properties
Color and Form: orange xtl
Molecular Weight: 586.01
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: not determined
Solubility in Water: insoluble

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SECTION 10: Stability and Reactivity
Stability: air and moisture stable
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: none
Incompatibility: oxidizing agents, halogens and active metals.
Decomposition Products: carbon monoxide, carbon dioxide, organic fumes, phosphorous pentoxide and ruthenium oxide.

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SECTION 11: Toxicological Information
RTECS Data: No information available in the RTECS files.
Carcinogenic Effects: No data
Mutagenic Effects: No data
Tetratogenic Effects: No data

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SECTION 12: Ecological Information
Ecological Information: No information available

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SECTION 13: Disposal Considerations
Disposal: Dispose of according to local, state and federal regulations.

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SECTION 14: Transportation
Shipping Name (CFR): Non-hazardous
Hazard Class (CFR): NA
Additional Hazard Class (CFR): NA
Packaging Group (CFR): NA
UN ID Number (CFR): NA
Shipping Name (IATA): Non-hazardous
Hazard Class (IATA): NA
Additional Hazard Class (IATA): NA
Packaging Group (IATA): NA
UN ID Number (IATA): NA

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SECTION 15: Regulatory Information
TSCA: Not listed in the TSCA inventory
SARA (Title 313): Title compound not listed
Second Ingredient: none

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  chloro(cyclopentadienyl)[bis(diphenylphosphino)methane]ruthenium 在 sodium 作用下， 以 甲醇 为溶剂， 以55%的产率得到Ru(H)(η(5)-cyclopentadienyl)(bis(diphenylphosphino)methane)
  参考文献：
  名称：

  Bruce, Michael I.; Humphrey, Mark G.; Swincer, A. Geoffrey, Australian Journal of Chemistry, 1984, vol. 37, p. 1747 - 1756

  摘要：

  DOI：
• 作为产物：
  描述：

  Ru(η5-cyclopentadienylato)(η6-naphthalene)(BF4) 、 苄基三乙基氯化铵 、 双二苯基膦甲烷 以 二氯甲烷 为溶剂， 反应 12.0h， 以70%的产率得到chloro(cyclopentadienyl)[bis(diphenylphosphino)methane]ruthenium
  参考文献：
  名称：

  [CpRu(C10H8)]+中萘置换合成钌半夹心配合物

  摘要：

  卤化物阴离子在钌配合物 [CpRu(C10H8)]+ (1) 中的萘配体置换很容易在室温下进行，得到不溶性低聚物质 [CpRuX]n (X = Cl, Br, I)。在单齿或双齿配体存在下的类似反应产生复合物 [CpRuL2X]，其中 L = CO, P(OMe)3, tBuNC；L2 = dppm、dppe、dppp、bipy、phen、cod、nbd 或 1,4-二苯基丁二烯。有用的催化剂 [CpRu(cod)X] 通过这种方法以 70-90% 的产率获得。[CpRu(cod)I] 的结构由 X 射线衍射确定。1 与 Br- 和烯丙基溴反应得到 RuIV 络合物 [CpRu(η3-C3H5)]Br2。还发现阳离子 1 在双齿膦存在下与叠氮化物阴离子反应得到 [CpRuL2N3] (L2 = dppm, dppe)。在不存在亲核阴离子的情况下，1 与中性配体的反应在可见光照射下进行，得到

  DOI：

  10.1002/ejic.201201112
• 作为试剂：
  描述：

  3-苯基丙酸 在 chloro(cyclopentadienyl)[bis(diphenylphosphino)methane]ruthenium 、 氢气 、 四苯硼钠 作用下， 以 甲苯 为溶剂， 160.0 ℃ 、8.0 MPa 条件下， 反应 24.0h， 以8%的产率得到3-苯基丙基 3-苯基丙酸酯
  参考文献：
  名称：

  カルボン酸化合物の水素化によるアルコールの製造方法、及び該製造方法に用いるルテニウム錯体

  摘要：

  使用均一系催化剂，以高效方式将羧酸化合物加氢转化为醇的方法。具体来说，在温和条件下，使用均一系催化剂，高效地将各种羧酸化合物加氢转化为醇的方法。解决方案是在特定的碱金属盐存在下，通过使用以RuMxNyPzq表示的钌配合物，将羧酸化合物加氢转化为醇的方法。【选择图】无

  公开号：

  JP2015124153A

文献信息

• Formation of Ammonia in the Reactions of a Tungsten Dinitrogen with Ruthenium Dihydrogen Complexes under Mild Reaction Conditions¹
  作者：Yoshiaki Nishibayashi、Shin Takemoto、Shotaro Iwai、Masanobu Hidai

  DOI：10.1021/ic000799f

  日期：2000.12.1

  trans-[RuHCl(dppp)2] (6). Free NH3 in 9-16% yields was observed in the reaction mixture, and further NH3 in 36-45% yields was released after base distillation. Detailed studies on the reaction of 5 with numerous Ru(eta 2-H2) complexes showed that the yield of NH3 produced critically depended upon the pKa value of the employed Ru(eta 2-H2) complexes. When 5 was treated with 10 equiv of trans-[RuCl(eta 2-H2)(dppe)2]X

  用反式-[RuCl（eta 2-H2）（dppp）2] X（3）（pKa = 4.4）和[RuCl（[2]）的平衡混合物处理顺-[W（N2）2（PMe2Ph）4]（5） dppp）2] X（4）[X = PF6，BF4或OTf；dppp = 1,3-双（二苯基膦基）丙烷]，在55℃，1 atm大气压的H2下，于苯二氯乙烷中含有10当量的基于钨的Ru原子，历时24 h，得到的NH3的总收率基于钨的45-55％ ，以及反式-[RuHCl（dppp）2]（6）的形成。在反应混合物中观察到游离NH 3的产率为9-16％，并且在碱蒸馏后进一步释放NH 3的产率为36-45％。对5与许多Ru（eta 2-H2）配合物的反应进行的详细研究表明，生成的NH3的产率关键取决于所用Ru（eta 2-H2）配合物的pKa值。当用10当量的反式[RuCl（eta 2-H2）（dppe）2] X（8）处理pKa =
• C−C Coupling Reactions of (Sulfene)ruthenium Complexes with Enolates
  作者：Wolfdieter A. Schenk、Jürgen Bezler

  DOI：10.1002/(sici)1099-0682(199805)1998:5<605::aid-ejic605>3.0.co;2-h

  日期：1998.5

  -ethane. Reaction of [CpRu(dppm)(SO2)]Cl (1d) and phenyldiazomethane gives the chlorobenzylsulfinato complex [CpRu(dppm)(SO2CHPhCl)] (3). Alternatively, 2a may be synthesized by sulfur dioxide addition to the carbene complex [CpRu(dppm)(CH2)]PF6 (5) which, in turn, is obtained from the corresponding methyl complex [CpRu(dppm)(CH3)] and [Ph3C]PF6. Treatment of 2a−d or 3 with the enolates of cyclic 2-methyl-1

  亚砜复合物 [CpRu(PR'3)2(RHC=SO2)]PF6 (2a-d) 从相应的二氧化硫复合物 1a-c 和重氮甲烷或 -乙烷中获得。[CpRu(dppm)(SO2)]Cl (1d) 和苯基重氮甲烷反应生成氯苄亚磺酸根络合物 [CpRu(dppm)(SO2CHPhCl)] (3)。或者，可以通过将二氧化硫加成到卡宾配合物 [CpRu(dppm)(CH2)]PF6 (5) 来合成 2a，而后者又是从相应的甲基配合物 [CpRu(dppm)(CH3)] 和 [ Ph3C]PF6。用环状 2-甲基-1,3-二酮、甲基丙二酸甲酯、开链氰基或β-氧代酯和环状β-氧代酯的烯醇化物处理2a-d或3得到C-C偶联产物6a， b, 7a-e, 8a-c, 9a-c 产率高，在一种情况下，也具有高非对映选择性。如此形成的官能化亚磺酸盐配体可被烷基化并随后通过配体用乙腈取代而从金属中心除去。MeCN/SO2交换后，钌络合物可以循环使用。
• Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes:  Toward a New Stereoselective Synthesis of Chiral Sulfoxides¹
  作者：Wolfdieter A. Schenk、Jürgen Frisch、Michael Dürr、Nicolai Burzlaff、Dietmar Stalke、Roland Fleischer、Waldemar Adam、Frank Prechtl、Alexander K. Smerz

  DOI：10.1021/ic961280f

  日期：1997.5.1

  orthorhombic system, space group P2(1)2(1)2(1) (No. 19), with a = 14.1664(13) Å, b = 15.792(2) Å, c = 17.641(2) Å, and Z = 4. 10b.0.93CH(2)Cl(2) crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), with a = 12.069(2) Å, b = 17.379(2) Å, c = 19.760(5) Å, and Z = 4. The thioether complexes can also be directly converted to sulfoxide complexes with the strong oxygen transfer reagent

  离子钌硫醚络合物[Cp（LL'）Ru（SRR'）] PF（6）（LL'= Ph（2）PCH（2）PPh（2）（1），Ph（2）PC（2）H（ 4）PPh（2）（2），（Ph（3）P，CO）（3），Me（2）PC（2）H（4）PPh（2）（4），（S，S）-Ph （2）PCHMeCHMePPh（2）（5），SRR'= MeSPh（a），MeS-i-Pr（b），MeSBz（c），i-PrSBz（d），EtSBz（e），MeSCy（f），由相应的氯配合物[Cp（LL'）RuCl]和硫醚合成了SC（4）H（8）（g））。5a在正交晶体系统中结晶，空间群P2（1）2（1）2（1）（第19号），a = 11.269（3）Å，b = 15.104（2）Å，c = 23.177（4） Å，Z =4。5b在单斜晶系空间群P2（1）（4号）中结晶，a = 10.539（5）Å，b = 16.216（9）Å，c
• Synthesis and structure of some ruthenium–rhenium heterodinuclear complexes and their catalytic activity in the addition of carboxylic acids to phenylacetylene
  作者：Suming Ye、Weng Kee Leong

  DOI：10.1016/j.jorganchem.2005.11.061

  日期：2006.3

  Cp*(CO)Ru(μ-H)[μ-PhP(C6H4)CH2PPh2]Re(CO)3, was also obtained from the first reaction. All these heterodinuclear products have been characterised crystallographically. They also showed good catalytic activity for the addition of carboxylic acids to phenylacetylene to afford the anti-Markovnikov products selectively.

  Na [Re（CO）5 ]与Cp * Ru（dppm）Cl，CpRu（dppm）Cl或CpRu（CO）2 Cl的盐消除反应得到异核物质Cp * Ru（μ-CO）2（μ- dppm）Re（CO）3，Cp（CO）Ru（μ-dppm）Re（CO）4或Cp（CO）2 RuRe（CO）5的产率中等。正金属化物种Cp *（CO）Ru（μ-H）[μ-PhP（C 6 H 4）CH 2 PPh 2 ] Re（CO）3也从第一反应获得。所有这些异双核产物均已通过晶体学表征。他们还显示出良好的催化活性，可以将羧酸加到苯乙炔中，从而选择性地提供抗马尔科夫尼科夫产物。
• Synthesis, characterization and reactivity of heterobimetallic complexes (η⁵-C₅R₅)Ru(CO)(μ-dppm)M(CO)₂(η⁵-C₅H₅) (R = H, CH₃; M = Mo, W). Interconversion of hydrogen/carbon dioxide and formic acid by these complexes
  作者：Man Lok Man、Zhongyuan Zhou、Siu Man Ng、Chak Po Lau

  DOI：10.1039/b306835h

  日期：——

  The heterobimetallic complexes [(η5-C5R5)Ru(CO)(μ-dppm)M(CO)2(η5-C5H5)] (M = Mo, W; R = H, CH3) (1–4) are prepared by metathetical reactions between (η5-C5R5)Ru(dppm)Cl and Na+[(η5-C5H5)M(CO)3]−. IR spectroscopic and X-ray structural studies show that each of these complexes contains a semi-bridging carbonyl ligand. The low activity of these complexes in catalytic CO2 hydrogenation to formic acid might be attributed to their non-facile reactions with H2 to yield the active dihydride species. The metal–metal bonds can be protonated to form the cationic complexes, which contain strong Ru–H–M bridges. The bridging hydrogen atom is weakly acidic since it can be removed by a strong base, and it protonates BPh4− to give BPh3 and benzene. It also reacts with the hydridic hydrogen of Et3SiH to yield H2. The bridging hydrogen, however, cannot be removed by hydride scavengers such as Ph3C+OTf− and Me3Si+OTf−. The sluggishness of the catalytic formic acid decomposition by 1–4 is attributable to the stability of the protonated bimetallic intermediate [(η5-C5R5)Ru(CO)(μ-dppm)(μ-H)M(CO)2(η5-C5H5)]+HCOO− formed during the catalysis.

  异二金属配合物[(δ-5-C5R5)Ru(CO)(δ-dppm)M(CO)2(δ-5-C5H5)]（M = Mo, W; R = H, CH3）（1â4）是通过(δ-5-C5R5)Ru(dppm)Cl和Na+[(δ-5-C5H5)M(CO)3]â之间的元反应制备的。红外光谱和 X 射线结构研究表明，这些复合物都含有一个半桥式羰基配体。这些配合物在催化 CO2 加氢生成甲酸过程中活性较低，这可能是由于它们与 H2 不容易发生反应生成活性二酸酐。金属与金属之间的键可以质子化，形成阳离子配合物，其中含有强 RuâHâM 桥。桥接氢原子具有弱酸性，因为它可以被强碱去除，并与 BPh4â 发生质子化反应，生成 BPh3 和苯。它还能与 Et3SiH 的氢桥原子反应生成 H2。然而，Ph3C+OTFâ 和 Me3Si+OTfâ 等氢化物清除剂无法清除桥氢。1â4 催化甲酸分解的缓慢性归因于催化过程中形成的质子化双金属中间体[(δ-5-C5R5)Ru(CO)(δ-dppm)(δ-H)M(CO)2(δ-5-C5H5)]+HCOOâ的稳定性。