二氯(N,N,N’,N’-四甲基乙二胺)钯 | 14267-08-4

• 物质功能分类: 有机原料 - 氨基化合物
• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 二氯(N,N,N’,N’-四甲基乙二胺)钯
• 中文别名: 二氯(N,N,N',N'-四甲基乙二胺)钯；顺-二氯(N,N,N`,N`-四甲基乙烯二胺)钯(II)；二氯(N,N,N′,N′-四甲基乙二胺)钯
• 英文名称: N,N,N',N'-tetramethylethylenediamine palladium(II) chloride
• 英文别名: Pd(TMEDA)Cl₂；[Pd(tetramethylethylenediamine)Cl₂]；dichloropalladium;N,N,N',N'-tetramethylethane-1,2-diamine
• CAS: 14267-08-4
• 化学式: C₆H₁₆Cl₂N₂Pd
• 分子量: 293.532
• InChiKey: FJOUSQLMIDWVAY-UHFFFAOYSA-L

物化性质

• 熔点：
  245 °C (dec.)(lit.)
• 稳定性/保质期：
  遵循规定使用和储存，则不会发生分解。

计算性质

• 辛醇/水分配系数(LogP)：
  -5.88
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S26,S37/39
• 危险类别码：
  R36/37/38
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H315,H319,H335
• 储存条件：
  存储于阴凉干燥环境。

SDS

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Section 1: Product Identification
Chemical Name: cis-Dichloro(N,N,N'N'-tetramethylethylenediamine)palladium(II), 99%
CAS Registry Number: 14267-08-4
Formula: C6H16Cl2N2Pd
EINECS Number: none
Chemical Family: organometallic complex
Synonym: cis-ichloroN,N,N',N'-Tetramethyl-ethane-1,2-diamine)palladium(II)

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 14267-08-4 100% 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: Ingestion, inhalation
Eye Contact: Causes slight to mild irritation of the eyes.
Skin Contact: Causes slight to 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. May be harmful if swallowed.
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: no data
Explosion Limits: no data
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 toxic organic 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: yellow powder
Molecular Weight: 293.53
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: strong oxidizing agents
Decomposition Products: carbon monoxide, carbon dioxide, palladium oxide and organic fumes

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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：

  二氯(N,N,N’,N’-四甲基乙二胺)钯 在 cesium fluoride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 3.05h， 生成 (TMEDA)Pd(CF₃)(Me)
  参考文献：
  名称：

  钯（II）三氟甲基配合物LPd（CF 3）X的一般前体（MeCN）2 Pd（CF 3）OTs的合成

  摘要：

  在钯催化的芳基-三氟甲基交叉偶联反应中，还原消除通常是限速步骤。还原消除的化学计量研究已证明有效地评估了各种配体促进这一具有挑战性的基本步骤的能力。然而，合成钯三氟甲基配合物的困难阻碍了该策略的使用。为了解决这一缺陷，我们在此报告了（MeCN）2 Pd（CF 3）OTs的合成，该化合物是空气和水分稳定的固体，可以用作访问各种LPd（CF 3的常见前体）X复合物。从这种配合物中，我们能够制备带有许多单膦，双膦和二胺配体的三氟甲基钯配合物，这些配体已知有助于促进Ar–CF 3和乙烯基–CF 3的还原消除。此外，我们发现通过修饰所用的NaX或AgX盐可以容易地改变阴离子配体（X）。

  DOI：

  10.1021/acs.organomet.9b00516
• 作为产物：
  描述：

  (N,N,N',N'-tetramethylethylenediamine)dimethylpalladium(II) 在 HCl 作用下， 以 甲苯 为溶剂， 以90%的产率得到二氯(N,N,N’,N’-四甲基乙二胺)钯
  参考文献：
  名称：

  二甲基（N，N，N'，N'-四甲基乙二胺）钯（II）和二甲基[1,2-双（二甲基膦基）乙烷]钯（II）：合成，X射线晶体结构以及热分解，氧化加成和配体交换反应

  摘要：

  DOI：

  10.1021/om00114a028
• 作为试剂：
  描述：

  4-溴-1,2-亚甲二氧基苯 、 2-异丙基-2-苯基乙腈 在 二氯(N,N,N’,N’-四甲基乙二胺)钯 、 四甲基乙二胺 、 (11bS)-N,N-bis((S)-1-Phenylethyl)-8,9,10,11,12,13,14,15-octahydrodinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine 、 lithium hexamethyldisilazane 作用下， 以 甲苯 为溶剂， 反应 24.17h， 以50%的产率得到(R)-2-(1,3-benzodioxol-5-yl)-3-methyl-2-phenylbutanonitrile
  参考文献：
  名称：

  钯催化的烷基腈的不对称α-芳基化

  摘要：

  烷基腈的不对称芳基化首次在良好的对映控制中形成四元立体中心。由烷基腈阴离子和二甲硅烷基酰胺离子组成的锂异二聚体是负责催化循环中立体确定金属转移的实际物质。

  DOI：

  10.1021/jacs.6b11610

文献信息

• An Efficient Method for Sterically Demanding Suzuki-Miyaura Coupling Reactions
  作者：Qing Zhao、Chengxi Li、Chris H. Senanayake、Wenjun Tang

  DOI：10.1002/chem.201203898

  日期：2013.2.11

  An efficient method for sterically demanding Suzuki–Miyaura coupling reactions has been developed with two catalysts, Pd/BI‐DIME (see scheme) and Pd/phenanthrene‐based ligand. The Pd/BI‐DIME catalyst facilitates the syntheses of extremely hindered biaryls bearing ortho‐isopropyl substituents. The other catalyst is efficient for the synthesis of functionalized tetra‐ortho‐substituted biaryls at low

  已经开发出了一种有效的空间要求苛刻的Suzuki-Miyaura偶联反应的方法，该方法使用两种催化剂，Pd / BI-DIME（参见方案）和Pd /菲基配体。Pd / BI-DIME催化剂促进了带有邻-异丙基取代基的受阻极强的芳基化合物的合成。另一种催化剂可在低催化剂负载下有效合成官能化的四邻位取代联芳基。
• Pd(II) Trifluoroacetate Complexes Containing Chelating Phosphine Ligands: Synthesis, Structures, and Catalysis
  作者：Kun-Woo Kim、Yong-Joo Kim、Hye Jin Lim、Soon W. Lee

  DOI：10.1002/bkcs.10590

  日期：2015.12

  which shows a Pd(II) metal, a DPPF ligand, and two CF3COO ligands. TwoCp rings in theDPPF ligand are not perfectly parallel,with a dihedral angle of 4.4(4) . ThePd Fe separation of 4.1932(8)A indicates no direct interactions between these two metals. We examined the ligand exchange reaction of complex 8 with 2 equiv of NaN3 in CH2Cl2 (Scheme 2). The reaction readily proceeded to give a Pd(II) azide complex

  羧酸盐通过它们的氧原子以末端、螯合或桥接的方式与过渡金属配位，并在各种催化反应中充当活性配体。众所周知，具有三氟乙酸盐 (TFA) 配体的过渡金属配合物比相应的乙酸盐对应物具有更高的溶解度和结晶度，具体取决于金属的特性。特别是，后过渡金属的 TFA 配合物是多种有机反应的有效催化剂，包括异氰化物或丁二烯的聚合以及 CO 和烯烃的共聚。此外，在有机底物的有氧氧化、乙烯基转移形成烯酰胺或在 Pd 催化剂存在下有机底物的氧化环化方面，这种配合物比相应的醋酸盐配合物表现出更高的效率。尽管已经报道了许多催化 Suzuki-Miyaura CC 偶联反应，但涉及后过渡金属-TFA 配合物的反应仍然很少见。出于这个原因，我们试图开发一种新的合成途径来合成具有螯合膦配体的 Pd-TFA 配合物，以用于这种偶联反应。在这项工作中，我们制备了一系列 Pd(II)-TFA-（螯合二膦）配合物，并研究了芳基卤化物和芳基硼​​酸的催化
• A New Class of Easily Activated Palladium Precatalysts for Facile C−N Cross-Coupling Reactions and the Low Temperature Oxidative Addition of Aryl Chlorides
  作者：Mark R. Biscoe、Brett P. Fors、Stephen L. Buchwald

  DOI：10.1021/ja801137k

  日期：2008.5.1

  one-component Pd precatalysts bearing biarylphosphine ligands is described. These precatalysts are air- and thermally stable, are easily activated under normal reaction conditions at or below room temperature, and ensure the formation of the highly active monoligated Pd(0) complex necessary for oxidative addition. The use of these precatalysts as a convenient source of LPd(0) in C-N cross-coupling reactions

  描述了一类新的带有联芳基膦配体的单组分 Pd 预催化剂。这些预催化剂对空气和热稳定，在室温或低于室温的正常反应条件下很容易活化，并确保形成氧化加成所需的高活性单连接 Pd(0) 络合物。探索了在 CN 交叉偶联反应中使用这些预催化剂作为 LPd(0) 的方便来源。本研究中展示的反应性在钯化学中是前所未有的。
• Synthesis of dinuclear palladium complexes having two parallel isocyanide ligands, and their application as catalysts to pyrrole formation from tert-butylisocyanide and alkynes
  作者：Naofumi Tsukada、Makiko Wada、Naoki Takahashi、Yoshio Inoue

  DOI：10.1016/j.jorganchem.2008.12.039

  日期：2009.4

  Novel dinuclear palladium complexes having two isocyanide ligands were synthesized by using a binucleating ligand, N,N′-bis[2-(diphenylphsphino)phenyl]formamidinate (dpfam). The structure of [Pd2(μ-dpfam)(tert-BuNC)2]Cl was confirmed by X-ray analysis, showing that the Pd–Pd bond length of 2.5824(3) Å falls well within the range of those for known dipalladium complexes having the edge-sharing structure

  通过使用双核配体N，N′-双[2-（二苯基膦基）苯基]甲ami酸盐（dpfam）合成具有两个异氰化物配体的新型双核钯配合物。的结构[钯2（μ -dpfam）（叔-BuNC）2 ]氯是由X射线分析确认，显示出的2.5824（3）钯-钯键长度的那些已知的范围内以及具有边缘共享结构和两个异氰化物的二钯配合物几乎平行且紧密地与钯配位。双核复合物[Pd 2（μ- dpfam）（tert -BuNC）2 ] PF 6用作由叔丁基异氰化物和各种炔烃形成吡咯的催化剂。
• Opposite influence of calf thymus DNA on the rate of substitution of ethylenediamine, by thiourea, in the complex cations [Pd(bpy)(en)]2+ and [Pd(bromazepam)(en)]2+ (bromazepam = 7-bromo-1,3-dihydro-5-(2-pyridyl)-2H-1,4-benzodiazepin-2-one)
  作者：Matteo Cusumano、Maria Letizia Di Pietro、Antonino Giannetto、Maria Anna Messina、Francesco Romano

  DOI：10.1039/a904471j

  日期：——

  Calf thymus DNA inhibits the substitution of ethylenediamine, by thiourea, in [Pd(bpy)(en)]2+ and catalyses the same reaction in [Pd(bromazepam)(en)]2+ (bromazepam = 7-bromo-1,3-dihydro-5-(2-pyridyl)-2H-1,4-benzodiazepin-2-one); this kinetic effect can be related to the different binding modes of the two complexes to the biopolymer.

  小牛胸腺DNA抑制乙烯二胺被硫脲在[Pd(bpy)(en)]2+中的取代反应，并催化同一反应在[Pd(bromazepam)(en)]2+中进行（bromazepam = 7-溴-1,3-二氢-5-(2-吡啶基)-2H-1,4-苯二氮杂卓-2-酮）；这一动力学效应与两种配合物在生物大分子上的不同结合模式有关。