对异丙苯基三环己基磷二氯化钌 | 145381-23-3

• 物质功能分类: 有机原料 - 有机金属类化合物 - 有机钌
• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: 对异丙苯基三环己基磷二氯化钌
• 中文别名: 对伞花烃(三环己基膦)二氯化钌
• 英文名称: (p-cymene)RuCl2(PCy3)
• 英文别名: RuCl2(PCy3)(η6-p-cymene)；1-Methyl-4-propan-2-ylbenzene;ruthenium(2+);tricyclohexylphosphane;dichloride；1-methyl-4-propan-2-ylbenzene;ruthenium(2+);tricyclohexylphosphane;dichloride
• CAS: 145381-23-3
• 化学式: C₂₈H₄₇Cl₂PRu
• 分子量: 586.631
• InChiKey: SKQOOGIJMPFDJH-UHFFFAOYSA-L

物化性质

• 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)：
  10.96
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 储存条件：
  存放在阴凉干燥处即可。

SDS

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Section 1: Product Identification
Chemical Name: Dichloro(p-cymene)tricyclohexylphosphineruthenium (II), min. 97%
CAS Registry Number: 145381-23-3
Formula: RuCl2(C10H14)P(C6H11)3
EINECS Number: none
Chemical Family: metal phosphine complex
Synonym: tricyclohexylphosphine(p-cymene)ruthenium dichloride

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 145381-23-3 100% 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: Inhalation, skin, eyes
Eye Contact: Causes slight to mild irritation of the eyes.
Skin Contact: Causes slight to mild 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 available 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 soap and water. Remove contaminated clothes if necessary. Seek medical
Skin Exposure:
assistance if 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: no data
Explosion Limits: no data
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 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 the material in a cool, dry, well ventilated place 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: If possible, handle the material in an efficient fume hood.
If ventilation is not available, a respirator should be worn. The use of respirators requires a Respiratory
Respirator:
Protection Program to be in compliance with 29 CFR 1910.134.
Ventilation: If possible, 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 powder
Molecular Weight: 586.62
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: none
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: Very strong oxidizing agents such as nitric acid may produce toxic volatile ruthenium tetroxide.
Incompatibility: oxidizing agents, halogens and active metals
Decomposition Products: carbon dioxide, carbon monoxide, organic fumes, phosphorus oxides, and ruthenium chloride.

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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 federal, state and local 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：

  对异丙苯基三环己基磷二氯化钌 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 2.5h， 以20%的产率得到[RuH2(η6-p-cymene)(P(C6H11)3)]
  参考文献：
  名称：

  钌催化未受约束的芳基-芳基键的还原裂解：反应发展和机理研究

  摘要：

  在一些重要的工业过程中发现了碳-碳键的断裂，例如石油裂解，并激发了许多合成方法的发展。然而，非极性无应变 C(芳基)-C(芳基)键仍然是最难被激活的键之一。作为对基本反应模式的详细研究，这里描述了我们开发的无应变 C(芳基)-C(芳基)键的 Ru 催化还原裂解的完整故事。在 2,2' 位置含有导向基团 (DG) 的多种联芳基化合物可作为有效底物。各种杂环，例如吡啶、喹啉、嘧啶和吡唑，可以用作DG。除氢气外，其他试剂，如汉茨酯、硅烷和醇类，也可用作末端还原剂。该反应的 pH 值为中性，不含氧化剂，因此可以容忍许多官能团。值得注意的是，已经实现了一锅 CC 激活/CC 耦合。计算和实验机理研究表明，该反应涉及一氢化钌（II）介导的 C（芳基）-C（芳基）活化，催化剂的静止状态是 η4 配位的二氯化钌（II）配合物，这可以激发基于该反应模式开发其他转化。

  DOI：

  10.1021/jacs.9b11605
• 作为产物：
  描述：

  dichloro(p-cymene)ruthenium(II) dimer 、 三环己基膦 以 二氯甲烷 为溶剂， 生成 对异丙苯基三环己基磷二氯化钌
  参考文献：
  名称：

  A most user-friendly protocol for ring closing metathesis reactions

  摘要：

  环闭合复分解反应（RCM）可通过光辅助方式便捷地实现，仅需在氖光下加热含有二烯底物、市售的[(p-枯烯)RuCl2]24和PCy3催化量的CH2Cl2溶液即可。

  DOI：

  10.1039/a808810a
• 作为试剂：
  描述：

  异喹啉 、 二乙基硅烷 在 对异丙苯基三环己基磷二氯化钌 作用下， 以 neat (no solvent) 为溶剂， 反应 18.0h， 以99%的产率得到2-(diethylsilyl)-1,2-dihydroisoquinoline
  参考文献：
  名称：

  钌（II）催化N-杂芳烃的区域选择性1，2-氢化硅烷化和T固键结合机理

  摘要：

  使用钌预催化剂[ Ru- （对-cymene）（PCy 3）Cl 2 ] 1实现了N-杂芳烃的高效区域选择性脱芳香化。反应在温和和纯净的条件下进行。多种N-杂芳烃在预催化剂1的存在下进行硅烷的加成反应，从而形成了独特的N-甲硅烷基-1,2-二氢杂芳烃产品。这种催化方法显示出较宽的底物范围。喹啉，异喹啉，苯并咪唑，喹喔啉，吡嗪，嘧啶和吡啶经历高度选择性的1,2-脱芳香化作用。N上的给电子和吸电子取代基-杂芳族化合物在该方案中具有良好的耐受性。机理研究表明在反应混合物中存在[ Ru- （对-cymene）（PCy 3）HCl] 4，这可能是催化剂的静止状态。密度泛函理论（DFT）研究揭示了完整的催化循环，表明产物的形成受N→Si锡rel键的控制。最初，PCy 3从1上解离，然后[（对-cymene）RuCl 2 ] 20与硅烷进一步反应，生成了催化活性中间体[（p- cymene）RuHCl]

  DOI：

  10.1021/acscatal.1c01148

文献信息

• Efficient Total Syntheses of Resin Glycosides and Analogues by Ring-Closing Olefin Metathesis
  作者：Alois Fürstner、Thomas Müller

  DOI：10.1021/ja991361l

  日期：1999.9.1

  presence of a catalyst formed from Ti(OiPr)4 and bis-(R,R)-trifluoromethanesulfonamide (9)), it was possible to achieve total syntheses of tricolorin A (1), tricolorin G (2), and jalapinolic acid (58) as well as the synthesis of the disaccharidic unit 48 which constitutes a common structural motif of all simonin, operculin, tuguajalapin, orizabin, mammoside, quamoclin, and stoloniferin resin glycosides

  概述了一种高效进入天然产物树脂糖苷家族的方法，它利用闭环复分解 (RCM) 的固有模块化特征来形成其大环内酯亚结构。仅从三个容易获得的糖构建块和 (6S)-undec-1-en-6-ol (7)（在由 Ti(OiPr)4 和双形成的催化剂存在下通过对映选择性加成二戊基锌到己烯醛制备-(R,R)-三氟甲磺酰胺(9))，可以实现三色苷A(1)、三色苷G(2)和墨西哥胡椒酸(58)的全合成以及双糖单元48的合成simonin、operculin、tuguajalapin、orizabin、mammoside、quamoclin 和 stoloniferin 树脂糖苷的共同结构基序。此外，这些天然存在的糖脂的各种类似物已经以简单的方式从同一组底物获得。这突出了所选方法和操作的灵活性...
• [RuCl₂(η⁶-p-cymene)] complexes bearing phosphinous acid ligands: preparation, application in C–H bond functionalization and mechanistic investigations
  作者：Lionel V. Graux、Michel Giorgi、Gérard Buono、Hervé Clavier

  DOI：10.1039/c5dt04683a

  日期：——

  [RuCl2(η6-p-cymene)] complexes bearing phosphinous acid (PA) ligands have been straightforwardly prepared from the dimer [RuCl2(p-cymene)]2 and secondary phosphine oxides (SPOs) and fully characterized. The steric parameter quantification of PAs, other L ligands and η6-p-cymene allowed a better comprehension of the coordination chemistry of these types of complexes and explained the absence of coordination in the

  一系列的合成将[RuCl 2（η 6 - p -cymene）]配合物轴承膦酸（PA）的配体已被直接地从二聚体制备将[RuCl 2（p -cymene）] 2和仲膦氧化物（SPOS）和完全表征。功率放大器，另一个L配体的位阻参数量化和η 6 - p -cymene允许这些类型的复合物的配位化学的一个更好的理解和解释了缺乏协调在笨重战略性计划目标的情况下，如Ad 2P（O）H。这些配合物在2-苯基吡啶的C–H活化/官能化中进行了测试，并在80°C时表现出最高的空间体积，获得了良好的活性。还研究了卤化物对钌配合物或对芳基卤化物伴侣的影响，显示出巨大的差异。卤化物作用的进一步研究特别是通过使用阳离子钌烷基环进行的，发现该钌是该反应的中间体。为了使次膦酸发挥的作用合理化，已提出了一种机制，该机制涉及次膦酸酯类所促进的协同金属化去质子化。
• Novel Ruthenium(II) N‐Heterocyclic Carbene Complexes as Catalyst Precursors for the Ring‐Opening Metathesis Polymerization (ROMP) of Enantiomerically Pure Monomers: X‐ray Structures, Reactivity, and Quantum Chemical Considerations
  作者：Michael R. Buchmeiser、Dongren Wang、Yan Zhang、Sergej Naumov、Klaus Wurst

  DOI：10.1002/ejic.200700041

  日期：2007.9

  tricyclohexylphosphane). X-ray structures of precatalysts 3 and 6–9 are presented. Compounds 3 and 4 displayed significant ROMP activity, allowing for the controlled, yet nonliving synthesis of the corresponding polymers with polydispersity indices (PDIs) in the range of 1.17–2.14. In all cases the exo isomers of compounds 1 and 2 were polymerized by preference. While poly(endo-1) was formed in an all-trans

  展示了预催化剂 3 和 6-9 的 X 射线结构。化合物 3 和 4 显示出显着的 ROMP 活性，允许以 1.17-2.14 的范围内的多分散指数 (PDI) 进行相应聚合物的受控但无生命的合成。在所有情况下，化合物1和2的外型异构体优选聚合。poly(endo-1) 是以全反式形式形成的，而 poly(exo-1) 和 poly(exo-2) 是以顺式/反式形式产生的，顺式含量约为 40%。在 B3LYP/LACVP* 水平上进行的计算表明，norborn-5-ene-2,3-dicarbimido 衍生物的 2,3-R2-exo,exo 异构体的反应性增加，导致形成 ROMP 的两种可能机制-活性RuIV亚烷基。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) 化合物 3 和 4 显示出显着的 ROMP
• Homobimetallic Ruthenium−Arene Complexes Bearing Vinylidene Ligands: Synthesis, Characterization, and Catalytic Application in Olefin Metathesis
  作者：Yannick Borguet、Xavier Sauvage、Guillermo Zaragoza、Albert Demonceau、Lionel Delaude

  DOI：10.1021/om1006177

  日期：2010.12.27

  almost equimolar proportion of cis and trans double bonds. No major changes were observed in the polymer yields and microstructures when complexes bearing donor groups on their aryl rings were employed as catalyst precursors. On the other hand, compounds bearing strongly electron-withdrawing substituents were significantly less active. Model vinylidene compound 5 and its ruthenium−ethylene parent (3)

  与取代基测距五个新arylvinylidene络合物从供电子强烈撤回（p -OMe，p -Me，p -Cl，p -CF 3，和米- （CF 3）2）以高收率通过使分离[（p -cymene）的Ru（μ-Cl）的3的RuCl（η 2 -C 2 H ^ 4）（PCY 3）]（3）与相应的苯乙炔衍生物。已知的苯基亚乙烯基配合物[（对-cymene）Ru（μ-Cl）3 RuCl（═C═CHPh）（PCy 3）]（5）也是在微波辐射下从[RuCl 2（p- cymene）] 2，三环己基膦和苯乙炔获得的。通过IR，NMR和XRD光谱学研究了远端芳基取代基对结构特征的影响。在亚乙烯基α-碳原子的化学位移与芳基取代基的Hammettσ-常数之间观察到非常好的线性关系。在各种类型的烯烃复分解反应中探讨了六种同双金属配合物的催化活性。未取代的苯基亚乙烯基化合物5用作这些实验的前导结构。它与降冰片烯的反应提供
• Cationic ruthenium allenylidene complexes as a new class of performing catalysts for ring closing metathesis
  作者：A. Fürstner、A. Fürstner、M. Picquet、C. Bruneau、P. H. Dixneuf

  DOI：10.1039/a803286f

  日期：——

  Cationic allenylidene ruthenium complexes [Ru CCCR2(L)(Cl)(arene)]PF6 (L = PCy3, PPri3), easily prepared from RuCl2(L)(p-cymene), prop-2-yn-1-ol and NaPF6, are found to be excellent catalyst precursors for ring closing olefin metathesis.

  研究发现，由 RuCl2(L)(p-cymene)、prop-2-yn-1-ol 和 NaPF6 容易制备的阳离子亚烯基钌配合物 [Ru CCCR2(L)(Cl)(arene)]PF6 （L = PCy3、PPri3）是用于闭环烯烃偏析反应的极佳催化剂前体。