chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II) | 92390-26-6

• 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 - 碳氢化合物 - 芳香烃
• 英文名称: chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II)
• 英文别名: (pentamethylcyclopentadienyl)Ru(1,5-cyclooctadiene)Cl；η5-C5Me5RuCl(1,5-cyclooctadiene)；(C5Me5)RuCl(cycloocta-1,5-diene)；Cp*RuCl(cod)；RuCl(cycloocta-1,5-diene)(C5Me5)；(pentamethylcyclopentadienyl)Ru(cod)Cl；(η5-C5Me5)RuCl(cod)；RuCl(cod)C5Me5；[Cp*Ru(cod)Cl]；(1Z,5Z)-cycloocta-1,5-diene;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;ruthenium(2+);chloride
• CAS: 92390-26-6
• 化学式: C₁₈H₂₇ClRu
• 分子量: 379.935
• InChiKey: PYZSVABUSHLGGV-ONEVTFJLSA-M

物化性质

• 熔点：
  143-147℃
• 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)：
  6.31
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• TSCA：
  No
• 危险等级：
  4.3
• WGK Germany：
  3
• 危险品运输编号：
  UN 3395
• 安全说明：
  S22,S36/37/39
• 危险类别码：
  R20/21/22
• 包装等级：
  II
• 危险类别：
  4.3
• 危险性防范说明：
  P231+P232,P280,P335+P334,P370+P378,P402+P404,P501
• 危险性描述：
  H261
• 储存条件：
  存放于阴凉干燥处。

SDS

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Section 1: Product Identification
Chemical Name: Chloro(1,5-cyclooctadiene)(pentamethylcyclopentadienyl)ruthenium (II), 98%
CAS Registry Number: 92390-26-6
Formula: RuCl(C8H12)(C10H15)
EINECS Number: none
Chemical Family: organometallic complex
Synonym: Chloro(pentamethylcyclopentadienyl)(1,5-cyclooctadiene)ruthenium

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 92390-26-6 100% no data no data

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Section 3: Hazards Identification
Emergency Overview: Irritating to the respiratory tract, skin and eyes. May be harmful if swallowed.
Primary Routes of Exposure: Ingestion, inhalation, skin, eyes
Eye Contact: Causes irritation of the eyes.
Skin Contact: Causes irritation of the skin.
Inhalation: Dust is irritating to the nose, mucous membranes and respiratory tract.
Ingestion: No specific information is available on the physiological effects of ingestion. May be harmful if swallowed.
Acute Health Affects: Irritating to skin, eyes and respiratory tract. May be harmful if swallowed.
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: none
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: carbon dioxide, dry powder or foam
If involved in a fire, fire fighters should be equipped with a NIOSH approved positive pressure self-contained
Special Fire Fighting Procedures:
breathing apparatus and full protective clothing.
Hazardous Combustion and If involved in a fire, this material may emit toxic 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 cold, in a tightly sealed container.

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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: brown microcrystals
Molecular Weight: 379.93
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 (store cold)
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(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II) 在 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 以88%的产率得到五甲基环戊二烯基双(三苯基膦)氯化钌(II)
  参考文献：
  名称：

  Luo, Lubin; Nolan, Steven P.; Fagan, Paul J., Organometallics, 1993, vol. 12, # 11, p. 4305 - 4311

  摘要：

  DOI：
• 作为产物：
  描述：

  (permethylcyclopentadienyl-methoxo-ruthenium)2 、 1,5-环辛二烯 在 LiCl 作用下， 以 乙醚 为溶剂， 以90%的产率得到chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II)
  参考文献：
  名称：

  Reaktionen von [Cp★RuOMe]2 VI. Ligandenaustausch unter komplexierender Deprotonierung zu und Molekülstruktur von (h4-1,5- Cyclooctadien)(h6-1,2,3,4-tetramethylfulven)ruthenium

  摘要：

  DOI：

  10.1016/0022-328x(90)85252-t
• 作为试剂：
  描述：

  5-hexenyl methanesulfonate 在 sodium azide 、 chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II) 作用下， 以 N,N-二甲基乙酰胺 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.5h， 生成
  参考文献：
  名称：

  米格他汀大三唑类化合物的合成及生物学评价

  摘要：

  报道了三种作为 migrastatin 类似物的大三唑的合成。该合成基于铜（I）-和钌催化的叠氮化物-炔环加成反应。通过使用 Trost 去对称化、Brown 烷氧基烯丙基化和有效的 Colvin 反应制备对映体纯末端炔衍生物。对产品的生物学评估表明，它在降低 MDA-MB-361 细胞系迁移能力方面具有良好的效果。

  DOI：

  10.1002/ejoc.201600988

文献信息

• Flexible Syntheses of Tripodal Phosphine Ligands 1,1,2-Tris(diarylphosphino)ethane and Their Ruthenium η⁵-C₅Me₅ Complexes
  作者：Peter E. Sues、Alan J. Lough、Robert H. Morris

  DOI：10.1021/om3005959

  日期：2012.9.24

  synthesized and coordinated to ruthenium to produce the complexes [Ru(η5-C5Me5)((PAr2)2CHCH2PAr2)]PF6 (2a–d) (Ar = phenyl (a), p-tolyl (b), o-tolyl (c), m-xylyl (d)). The 1,1,2-tris(diarylphosphino)ethane compounds were generated in a novel trisubstitution reaction of diarylphosphorylacetaldehyde diethyl acetal, a useful synthetic precursor that was used previously for the synthesis of phosphonium dimers.

  一系列的四个三足多膦配位体（PAR 2）2 CHCH 2 PAR 2（1A - d）的合成和配位到钌以产生复合物的[Ru（η 5 -C 5我5）（（PAR 2）2 CHCH 2 PAR 2）] PF 6（2A - d）（Ar为苯基（一），p -甲苯基（b），Ô甲苯基（ç），米-二甲苯（d））。1,1,2-三（二芳基膦基）乙烷化合物是在二芳基磷酰基乙醛二乙基乙缩醛的新型三取代反应中生成的，该化合物是有用的合成前体，以前用于合成phospho二聚体。该三齿配体随后用的钌（II）前体的Ru组合（η 5 -C 5我5）（1,5-COD）氯，以探针的配位几何形状1A - d。将得到的复合物2A - d显示其中的膦配体是在一个配位钢琴凳型结构FAC几何学。尽管配体的空间很大，并且由于形成了一个以钌为中心的四元环和两个五元环而引起的环应变，但配合物2a - d相当稳定。钌盐是空气和水分稳定的，即使在高温下也不会与CO，H
• Novel half-sandwich η⁵ -Cp *-rhodium(III) and η⁵ -Cp *-ruthenium(II) complexes bearing bis(phosphino)amine ligands and their use in the transfer hydrogenation of aromatic ketones
  作者：Fatih Ok、Murat Aydemir、Feyyaz Durap、Akın Baysal

  DOI：10.1002/aoc.3068

  日期：2014.1

  Two new half‐sandwich η5‐Cp*–rhodium(III) and η5‐Cp*–ruthenium(II) complexes have been prepared from corresponding bis(phosphino)amine ligands, thiophene‐2‐(N,N‐bis(diphenylphosphino)methylamine) or furfuryl‐2‐(N,N‐bis(diphenylphosphino)amine). Structures of the new complexes have been elucidated by multinuclear one‐ and two‐dimensional NMR spectroscopy, elemental analysis and IR spectroscopy. These

  两个新的半夹心η 5 -Cp * -铑（III）和η 5 -Cp * -钌（II）络合物已经从相应的双（膦）胺配体来制备，噻吩-2-（Ñ，Ñ双（二苯基膦基甲胺）或糠基-2-（N，N-双（二苯基膦基）胺）。通过多核一维和二维NMR光谱，元素分析和IR光谱阐明了新络合物的结构。这些带有双（膦）胺配体的Cp *-铑（III）和Cp *-钌（II）配合物已成功地用于转移2-丙醇对各种酮的氢化作用。版权所有©2013 John Wiley＆Sons，Ltd.
• Half-Sandwich Ruthenium Carbene Complexes Link<i>trans</i>-Hydrogenation and<i>gem</i>-Hydrogenation of Internal Alkynes
  作者：Alexandre Guthertz、Markus Leutzsch、Lawrence M. Wolf、Puneet Gupta、Stephan M. Rummelt、Richard Goddard、Christophe Farès、Walter Thiel、Alois Fürstner

  DOI：10.1021/jacs.8b00665

  日期：2018.2.28

  E-alkenes are formed by trans-delivery of the two H atoms of H2. A combined experimental and computational study now provides a comprehensive mechanistic picture: a metallacyclopropene (η2-vinyl complex) is primarily formed, which either evolves into the E-alkene via a concerted process or reacts to give a half-sandwich ruthenium carbene; in this case, one of the C atoms of the starting alkyne is converted

  用 [Cp*Ru] 基催化剂对内部炔烃进行氢化的特点是非正统的立体化学过程，因为 E-烯烃是通过 H2 的两个 H 原子的反式传递形成的。一项结合实验和计算的研究现在提供了一个全面的机理图：主要形成金属环丙烯（η2-乙烯基配合物），它要么通过协同过程演变成 E-烯烃，要么反应生成半夹心钌卡宾；在这种情况下，起始炔烃的一个碳原子被转化为亚甲基。这种转变代表了 π 键的正式宝石氢化，这几乎没有任何先例。反式氢化和宝石氢化的障碍相似：而 DFT 预测偏向于反式氢化，而 CCSD(T) 发现宝石氢化稍微容易一些。卡宾一旦形成，将结合第二个 H2 分子并演变成所需的 E-烯烃、位置烯烃异构体或相应的烷烃；这种缔合途径解释了为什么双键异构化和过度还原与反式氢化竞争。计算的场景与副氢诱导极化转移 (PHIP) NMR 数据一致，该数据证实了 H2 的直接传递、通过 gem-氢化形成卡宾中间体，以及它们向
• Optically active transition-metal complexes VII Iron and ruthenium complexes with the optically active cyclopentadienyl ligand PCp: syntheses and ligand exchange reactions
  作者：Bernhard Pfister、Ruedi Stauber、Albrecht Salzer

  DOI：10.1016/s0022-328x(96)06849-0

  日期：1997.4

  The optically active complexes [PCpFe(CO)2]2 and [PCpRu(CO)2]2 (PCp = pinene-fused cyclopentadiene) have been converted into half-sandwich complexes PCpM(CO)2X (XCl, Br, I, CH3, COMe, COPh, COMes) by either oxidative or reductive methods. Ligand exchange of one of the diastereotopic carbonyl ligands for a Lewis base L L = tertiary phosphine or phosphite) generates diastereomeric complexes PCpML(CO)X

  旋光配合物[PCpFe（CO）2 ] 2和[PCpRu（CO）2 ] 2（PCp = pin烯稠合的环戊二烯）已转化为半三明治复合物PCpM（CO）2 X（XCl，Br， I，CH 3，COMe，COPh，COMes）通过氧化或还原方法。Lewis碱LL =叔膦或亚磷酸酯的非对映体羰基配体之一的配体交换产生在金属中心具有拟四面体手性的非对映体复合物PCpML（CO）X。非对映异构体比例随着新配体的空间体积的增加而增加，其上限为64％de。使用MRu，对于X =卤素，配位体交换的光化学方法和热方法都可能，不仅会导致非对映异构体的比例不同，而且会导致其非对映异构体的反向比例增加。通过热配体交换产生的光诱导明显更高，并且被证明是热力学起源的。
• Ruthenium(II)-Catalyzed Selective Intramolecular [2 + 2 + 2] Alkyne Cyclotrimerizations
  作者：Yoshihiko Yamamoto、Takayasu Arakawa、Ryuji Ogawa、Kenji Itoh

  DOI：10.1021/ja0358697

  日期：2003.10.1

  containing functional groups such as ester, ketone, nitrile, amine, alcohol, sulfide, etc. can be used for the present ruthenium catalysis. The most significant advantage of this protocol is that the cycloaddition of unsymmetrical 1,6-diynes with one internal alkyne moiety regioselectively gave rise to meta-substituted products with excellent regioselectivity. Completely intramolecular alkyne cyclotrimerization

  在催化量的 Cp*RuCl(cod) 存在下，1,6-二炔在环境温度下与单炔进行化学选择性反应，以良好的产率得到所需的双环苯衍生物。多种含有官能团如酯、酮、腈、胺、醇、硫化物等的二炔和单炔可用于本发明的钌催化。该协议最显着的优点是不对称 1,6-二炔与一个内部炔烃部分的环加成区域选择性产生了具有优异区域选择性的间位取代产品。完全分子内炔烃环三聚也使用三炔底物完成，以获得与 5-7 元环稠合的三环芳族化合物。与这些环三聚反应相关的 ruthenabicycle 复合物是由 Cp*RuCl(cod) 和具有苯基端基的 1,6-二炔合成的，其结构由 X 射线分析明确确定。这种钌环中间体的中间体通过它与乙炔的反应得到了进一步证实，产生了预期的环加合物。环三聚机制的密度泛函研究表明，环三聚通过氧化环化进行，产生一个钌环中间体，随后由合成的钌环与炔烃的正式 [2 + 2] 环加成引发的炔烃插入。这种钌