RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) | 246047-72-3

• 物质功能分类: 化学试剂 - 有机试剂 - 膦配体
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh)
• 英文别名: 2nd generation grubbs catalyst；1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene-dichloro(phenylmethylene)-(tricyclohexyl-phosphine)ruthenium；Ru(CHPh)(PCy3)Cl2(1,3-(2,4,6-Me3C6H2)2-imidazolidin-2-yl)；(benzylidene)(PCy3)RuCl2(C3H5N2(Mes)2)；tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene]ruthenium(IV)dichloride；[(1,3-bis(2,4,6-Me3-Ph)imidazolidin-2-yl)][PCy3][=CHPh]RuCl2；{[P(c-hexyl)3](1,3-dimesitylimidazolidin-2-yl)Ru(=CHPh)Cl2}；Grubbs II ruthenium metathesis catalyst；Grubbs catalyst 2nd generation；{PhCH=RuCl2[P(cyclohexyl)3][N,N'-bis(Mes)imidazolidin-2-yl]}；{(PCy3)Cl2(Ph-CH=)Ru[-CH(-N(Mes)CH2CH2N(Mes)-)]}；Grubbs' imidazolium catalyst；(PCy3)(Im(Mes)2)Ru=CHPh；Grubbs' type II；Grubbs ruthenium-based catalyst 2nd generation；Grubbs' second-generation carbene catalyst；second generation Grubbs' catalyst；Grubbs' 2nd generation catalyst；Ru(H2IMes)Cl2PCy3(=CHPh)；dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II)；Grubbs II
• CAS: 246047-72-3
• 化学式: C₄₆H₆₅Cl₂N₂PRu
• 分子量: 848.985
• InChiKey: FCDPQMAOJARMTG-UHFFFAOYSA-L

物化性质

• 熔点：
  143.5-148.5 °C(lit.)
• 溶解度：
  氯仿（少量溶解）、乙酸乙酯（少量溶解）、甲醇（极少量，加热）
• 稳定性/保质期：
  该试剂对空气和湿气较为稳定，在空气中不会分解，且其催化活性不受溶剂中空气、水蒸气及微量杂质的影响。

计算性质

• 辛醇/水分配系数(LogP)：
  13.73
• 重原子数：
  52
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险等级：
  4.1
• 危险品标志：
  F
• 安全说明：
  S26,S36/37/39
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 危险品运输编号：
  UN1325 - class 4.1 - PG 2 - Flammable solids, organic, n.o.s., HI： all
• 包装等级：
  Ⅱ
• 危险标志：
  GHS02
• 危险性描述：
  H228
• 危险性防范说明：
  P210
• 危险类别：
  4.1
• 储存条件：
  2-8°C

SDS

Name:	Grubb s second generation catalyst 97% Material Safety Data Sheet
Synonym:
CAS:	246047-72-3

Section 1 - Chemical Product MSDS Name:Grubb s second generation catalyst 97% Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
246047-72-3	Grubb's second generation catalyst	97%	unlisted

Hazard Symbols: None Listed.
Risk Phrases: None Listed.

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Air sensitive.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation. May be harmful if absorbed through the skin.
Ingestion:
May cause irritation of the digestive tract. May be harmful if swallowed.
Inhalation:
May cause respiratory tract irritation. May be harmful if inhaled.
Chronic:
Not available.

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Section 4 - FIRST AID MEASURES
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes.
Ingestion:
Get medical aid. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately.
Notes to Physician:
Treat symptomatically and supportively.

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Vacuum or sweep up material and place into a suitable disposal container.

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Section 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes. Use and store under nitrogen.
Storage:
Store in a cool, dry place. Store in a tightly closed container.
Store under nitrogen.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 246047-72-3: Personal Protective Equipment Eyes: Not available.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Crystals
Color: pink to brown
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: Insoluble.
Specific Gravity/Density:
Molecular Formula: C46H65Cl2N2PRu
Molecular Weight: 848.99

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable.
Conditions to Avoid:
Incompatible materials, exposure to air.
Incompatibilities with Other Materials:
Oxidizing agents, halogens, active metals.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide, hydrocarbons, ruthenium oxide.
Hazardous Polymerization: Will not occur.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 246047-72-3 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Grubb's second generation catalyst - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

IATA
Not regulated as a hazardous material.
IMO
Not regulated as a hazardous material.
RID/ADR
No information available.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: Not available.
Risk Phrases:
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
WGK (Water Danger/Protection)
CAS# 246047-72-3: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 246047-72-3 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 246047-72-3 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

背景 烯烃复分解反应是有机化学中最为重要和实用的一类反应，它使通常难以反应的双键能够彼此偶联，极大地拓展了构造化合物骨架的可能性。由于这种反应条件温和、产率高，并且绝大多数有机基团在这一过程中无需保护，近年来受到了学术界和工业界的广泛重视。金属卡宾化合物因其能有效催化各种类型的烯烃复分解反应而备受关注，尤其是Grubbs催化剂。

简介 Grubbs催化剂是一种用于烯烃复分解反应的配位化合物，其配体对催化剂的性能和稳定性有很大影响。

特性 Grubbs二代催化剂通过将第一代催化剂中的三环己基膦配体替换为二取代二氢咪唑配体而制得。这种配体中氮原子取代基的空间位阻效应和电子效应使得Grubbs二代催化剂在反应过程中更为稳定，不易发生分解。与第一代催化剂相比，它不仅具有更强的稳定性，还表现出更高的反应活性。

设计理念 Grubbs二代催化剂的设计理念是用比磷配体具有更强给电子能力和更高稳定性的N-杂环卡宾配体取代其中一个磷配体。

用途 相比于第一代催化剂，Grubbs第二代催化剂更具活性且能广泛应用于不同类型的底物，包括对空间有要求或容易失活的烯烃，如1,1 - 二取代烯烃和α，β-不饱和羰基化合物。

反应信息

• 作为反应物：
  描述：

  RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以95%的产率得到(2R,4aR,5aS,10aR,11R,11aS)-2-(naphthalen-2-yl)-4,4a,5a,6,9,10a,11,11a-octahydro-[1,3]dioxino[40,50:5,6]pyrano[3,2-b]oxepin-11-ol
  参考文献：
  名称：

  Ciguatoxin 3C ABCDEF环的合成

  摘要：

  瓜瓜毒素3C ABCDEF环的合成是通过以下途径实现的，该方法包括将对应于AB环的二甲基二硫缩醛单-S-氧化物衍生物和对应于EF环的醛进行阴离子偶联，然后使用还原醚化进行环化。AB-环是从已知的基于闭环烯烃复分解的d-葡萄糖衍生物合成的，而EF-环是通过采用手性转移爱尔兰-克莱森重排和闭环烯烃复分解的方法制备的。

  DOI：

  10.1016/j.tet.2016.12.041
• 作为产物：
  描述：

  在 甲酸 、 potassium tert-butylate 作用下， 以 正己烷 为溶剂， 反应 29.0h， 生成 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh)
  参考文献：
  名称：

  Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts

  摘要：

  该发明涉及将8族过渡金属卡宾配合物用作烯烃交叉⽐特⽅反应的催化剂。具体地，使用取代有N-杂环卡宾配体的钌和锇烷基亚烯配合物来催化交叉⽐特⽅反应，从而提供各种取代和官能化的烯烃，包括磷酸酯取代的烯烃，直接卤代的烯烃，1,1,2-三取代的烯烃和季铵烯烃。该发明还提供了一种利用上述配合物催化第一烯烃反应物（可能带有或不带有官能团）与多种不同烯烃反应物（可能带有或不带有官能团）进行交叉⽐特⽅反应，从而得到多种结构不同的烯烃产物的方法。该发明的方法还有助于促进顺式构型的1,2-二取代烯烃的立体选择性合成。

  公开号：

  US09403854B2
• 作为试剂：
  描述：

  5-(allyloxy)-2,2-dimethyl-8-phenyl-2H,6H-pyrano[3,2-g]chromen-6-one 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 作用下， 以 二氯甲烷 为溶剂， 反应 5.5h， 生成
  参考文献：
  名称：

  Osajin、Scandenone 及其类似物的全合成及抗炎评价

  摘要：

  本研究完成了osajin、scandenone及其类似物的全合成。关键的合成步骤包括羟醛/分子内碘醚化/消除序列反应和铃木偶联反应以组装三环核心，化学选择性炔丙基化和克莱森重排反应以获得天然化合物。此外，我们还设计合成了二十五种天然产物类似物。所有合成化合物均在脂多糖 (LPS) 刺激的 RAW264.7 巨噬细胞中筛选针对肿瘤坏死因子-α (TNF-α) 和白细胞介素 6 (IL-6) 的抗炎活性。总的来说，化合物 39e 和 39d 被认为是有希望进一步开发的先导化合物。

  DOI：

  10.3390/ph17010086

文献信息

• Tandem Catalysis:  The Sequential Mediation of Olefin Metathesis, Hydrogenation, and Hydrogen Transfer with Single-Component Ru Complexes
  作者：Janis Louie、Christopher W. Bielawski、Robert H. Grubbs

  DOI：10.1021/ja016431e

  日期：2001.11.1

  extensive use in olefin metathesis, it was also recently shown to be an effective precatalyst for mediating radical additions and hydrogenation reactions. We recently demonstrated all three reactions could be performed in tandem to afford well-defined block copolymers. Herein, we report that complex 1, or its more active derivative 2, is also useful in mediating a variety of other catalytic hydrogenation

  有机金属催化剂传统上被设计和优化以介导单一反应。然而，对方便有效的合成过程日益增长的需求需要开发能够直接或通过简单修饰催化多种机械不同反应的有机金属试剂。虽然 Ru 配合物 (PCy_3)_2Cl_2Ru= CHPh (1) 在烯烃复分解中得到了广泛的应用，但最近它也被证明是一种有效的预催化剂，用于介导自由基加成和加氢反应。我们最近证明了所有三个反应都可以串联进行，以提供明确定义的嵌段共聚物。在此，我们报告复合体 1，或其更活跃的衍生物 2，也可用于介导各种其他催化氢化反应，包括区域特异性酮和烯烃还原、酮的转移氢化和醇的脱氢氧化。此外，我们展示了各种用于快速构建小分子的“一锅”串联复分解加氢程序，包括 (R)-(-)-Muscone。
• Direct synthesis of dialkylarylvinylsilane derivatives: metathesis of dialkylaryl-iso-propenylsilane and its application to tetracyclic silacycle dye synthesis
  作者：Shohei Yoshioka、Tsunayoshi Takehara、Tsuyoshi Matsuzaki、Takeyuki Suzuki、Hirofumi Tsujino、Tadayuki Uno、Yasuo Tsutsumi、Kenichi Murai、Hiromichi Fujioka、Mitsuhiro Arisawa

  DOI：10.1039/c9cc06777a

  日期：——

  The metathesis of dialkylarylvinylsilane, which has not been accomplished to date, is achieved using dialkylaryl-iso-propenylsilane as a substrate. In addition, we discovered that the reason why the metathesis of a ruthenium carbene complex and dialkylarylvinylsilane is difficult is the formation of a carbide complex.

  使用二烷基芳基-异丙烯基硅烷作为底物可以实现迄今为止尚未完成的二烷基芳基乙烯基硅烷的复分解反应。另外，我们发现钌卡宾配合物和二烷基芳基乙烯基硅烷难以复分解的原因是碳化物配合物的形成。
• Phosphinate ruthenium complexes
  申请人：Idenix Pharmaceuticals, Inc.

  公开号：US09115095B2

  公开（公告）日：2015-08-25

  Provided herein are ruthenium complexes of Formula I, and processes of preparation thereof. Also provided are methods of their use as a metathesis catalyst.

  本文提供了一种一式的钌配合物，以及其制备方法。还提供了它们作为交换催化剂的使用方法。
• Kinetics and Mechanism of Isocyanide-Promoted Carbene Insertion into the Aryl Substituent of an N-Heterocyclic Carbene Ligand in Ruthenium-Based Metathesis Catalysts
  作者：Justin R. Griffiths、Elan J. Hofman、Jerome B. Keister、Steven T. Diver

  DOI：10.1021/acs.organomet.7b00342

  日期：2017.8.28

  In situ IR spectroscopy was used to study the kinetics of addition of L = alkyl and aryl isocyanides to the Grubbs second-generation carbene complex Ru(H2IMes)(CHPh)(PCy3)Cl2 (H2IMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene), which triggers carbene insertion into an aromatic ring of the N-heterocyclic carbene supporting ligand, forming Ru1-mesityl-3-(7′-Ph-2′,4′,6′-trimethylcycloheptatrienyl)-4

  使用原位红外光谱研究了将L =烷基和芳基异氰酸酯添加到Grubbs第二代卡宾络合物Ru（H 2 IMes）（CHPh）（PCy 3）Cl 2（H 2 IMes = 1,3 -dimesityl-4,5-dihydroimidazol-2-ylidene），触发卡宾插入N杂环卡宾支持配体的芳香环，形成Ru 1-mesityl-3-（7'-Ph-2'，4 ′，6′-三甲基环庚三烯基）-4，5-二氢咪唑-2-亚基} L 2（PCy 3）Cl 2。速率定律被确定为异氰化物浓度为一阶，卡宾络合物浓度为一阶。对于各种异氰化物，CNR的比率随着R =叔数的增加而增加丁基≪环己基<正辛基
• [EN] NOVEL TRANSITION METAL COMPLEXES, THEIR PREPARATION AND USE<br/>[FR] NOUVEAUX COMPLEXES DE MÉTAUX DE TRANSITION, LEUR PRÉPARATION ET UTILISATION
  申请人：LANXESS DEUTSCHLAND GMBH

  公开号：WO2014187973A1

  公开（公告）日：2014-11-27

  Novel transition metal complexes are provided which represent viable catalysts for a broad variety of reactions such as hydrogenation reactions and metathesis reactions. Novel preparation processes are made available via unprecedented routes inter alia not involving structures according to Grubbs I or Grubbs II catalysts.

  提供了新型过渡金属配合物，这些配合物可作为广泛反应的催化剂，如加氢反应和醇醚交换反应。通过前所未有的途径提供了新颖的制备方法，其中不涉及Grubbs I或Grubbs II催化剂的结构。