四(亚磷酸三苯酯)镍 | 14221-00-2

• 物质功能分类: 有机原料 - 有机金属类化合物 - 有机镍
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 四(亚磷酸三苯酯)镍
• 中文别名: 四(三苯基亚磷酸盐)镍；四-(三磷酸三苯酯)镍(0)；三苯酚丙烯酸甲酯
• 英文名称: tetrakis(triphenylphosphite)nickel(0)
• 英文别名: Ni[P(OPh)₃]₄；nickel tetrakis(triphenylphosphite)；nickel;triphenyl phosphite
• CAS: 14221-00-2
• 化学式: C₇₂H₆₀NiO₁₂P₄
• 分子量: 1299.85
• InChiKey: PGXCIAAANFTEKX-UHFFFAOYSA-N

物化性质

• 熔点：
  145 °C (dec.)(lit.)

计算性质

• 辛醇/水分配系数(LogP)：
  21.8
• 重原子数：
  89
• 可旋转键数：
  24
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  111
• 氢给体数：
  0
• 氢受体数：
  12

安全信息

• 危险品标志：
  Xn
• 安全说明：
  S26,S36/37
• 危险类别码：
  R40,R36/37/38,R43
• WGK Germany：
  3
• 海关编码：
  29209090
• 储存条件：
  | 冰箱 (+4℃) |

SDS

Name:	Tetrakis(triphenyl phosphite)nickel(0) Material Safety Data Sheet
Synonym:
CAS:	14221-00-2

Section 1 - Chemical Product MSDS Name:Tetrakis(triphenyl phosphite)nickel(0) Material Safety Data Sheet
Synonym:

---

Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
14221-00-2	Tetrakis(triphenyl phosphite)nickel(0)		unlisted

Hazard Symbols: XN
Risk Phrases: 36/37/38 40 42/43

---

Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Irritating to eyes, respiratory system and skin. Limited evidence of a carcinogenic effect. May cause sensitization by inhalation and skin contact.Air sensitive.
Potential Health Effects
Eye:
Causes eye irritation.
Skin:
Causes skin irritation. May be harmful if absorbed through the skin.
May cause sensitization by skin contact.
Ingestion:
May cause irritation of the digestive tract. May be harmful if swallowed.
Inhalation:
Causes respiratory tract irritation. May be harmful if inhaled.
Chronic:
Possible risk of irreversible effects.

---

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. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:
Treat symptomatically and supportively.

---

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.

---

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.

---

Section 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes. Use only in a chemical fume hood.
Storage:
Store in a tightly closed container. Keep refrigerated. (Store below 4C/39F.) Store under nitrogen.

---

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# 14221-00-2: 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.

---

Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Powder
Color: tan
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 145 deg C (dec)
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C72H64NiO12P4
Molecular Weight: 1303.026

---

Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not available.
Conditions to Avoid:
Incompatible materials, exposure to air.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, oxides of phosphorus, carbon dioxide, nickel oxide.
Hazardous Polymerization: Has not been reported

---

Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 14221-00-2 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Tetrakis(triphenyl phosphite)nickel(0) - California: carcinogen, initial date 5/7/04 (listed as Nickel compound NTP: Known carcinogen (listed as Nickel compounds).
IARC: Group 1 carcinogen (listed as Nickel compounds).

---

Section 12 - ECOLOGICAL INFORMATION

---

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

---

Section 14 - TRANSPORT INFORMATION

IATA
No information available.
IMO
No information available.
RID/ADR
No information available.

---

Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XN
Risk Phrases:
R 36/37/38 Irritating to eyes, respiratory system
and skin.
R 40 Limited evidence of a carcinogenic effect.
R 42/43 May cause sensitization by inhalation and
skin contact.
Safety Phrases:
S 22 Do not breathe dust.
S 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 36/37/39 Wear suitable protective clothing, gloves
and eye/face protection.
S 45 In case of accident or if you feel unwell, seek
medical advice immediately (show the label where
possible).
WGK (Water Danger/Protection)
CAS# 14221-00-2: No information available.
Canada
CAS# 14221-00-2 is listed on Canada's NDSL List.
CAS# 14221-00-2 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 14221-00-2 is listed on the TSCA inventory.

---

SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  四(亚磷酸三苯酯)镍 、 碘化氰 以 二氯甲烷 、 正戊烷 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Bobadilla, M.; Moran, M., Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1983, vol. 38, # 9, p. 1069 - 1071

  摘要：

  DOI：
• 作为产物：
  描述：

  亚磷酸三苯酯 、 nickel(II) nitrate hexahydrate 在 sodium tetrahydroborate 作用下， 以 乙腈 为溶剂， 以46%的产率得到四(亚磷酸三苯酯)镍
  参考文献：
  名称：

  四面体镍（0）配合物的合成和发光性质

  摘要：

  四面体镍（0）络合物[NiL 4 ]，[Ni（dppe）2 ]和[Ni（CO）2（SbPh 3）2 ]（L = AsPh 3，SbPh 3，P（OPh）3，dppe = 1，通过在配体存在下在N 2或CO气氛下用NaBH 4还原NiCl 2 ·6H 2 O制备2-双（二苯基膦基）乙烷。NiCl 2 ·6H 2 O / SbPh 3体系在铂金丝网上于-1.3 V（Ag / Ag +）电解得到复合物[Ni（SbPh 3）4 ]。（摩尔比＝ 1：4）。这些复合物，无论是固态还是溶液，当被紫外线辐射激发时，在室温下均呈橙色发射。提出了[NiL 4 ]配合物的定性分子轨道图。配合物的电子吸收光谱显示出在400 nm附近的谱带，被指定为MLCTπ∗ 2e ←d 2t2。建议在这些系统中观察到的发射具有1 A 1 ← 3 T 1跃迁。根据时间分辨的发射光谱估算了微秒范围内的寿命。还研究了游离配体的光谱性质。

  DOI：

  10.1016/s0020-1693(96)05335-2
• 作为试剂：
  描述：

  2-(penta-1,2-dien-1-yl)-1-(phenylsulfonyl)-1H-indole 、 丙酮氰醇 在 四(亚磷酸三苯酯)镍 、 二苯基-2-吡啶膦 作用下， 以 甲苯 为溶剂， 反应 0.33h， 以53%的产率得到(E)-2-ethyl-4-(1-(phenylsulfonyl)-1H-indol-2-yl)but-3-enenitrile
  参考文献：
  名称：

  通过芳基烯丙基的区域和立体选择性氢氰化形式（±）-quebrachamine的形式合成

  摘要：

  本文介绍了基于1,3-二取代的烯基的区域和立体选择性氢氰化的邻苯二甲胺的形式合成。通过Ni催化的氢氰化作用有效地区分了烯基C C双键，并且CN基团被用作哌啶环的合成子。从HCN加合物开始的几个步骤提供了邻苯二甲酰胺的已知中间体。

  DOI：

  10.1016/j.tet.2018.04.044

文献信息

• Stable Nickel(0) Phosphites as Catalysts for CN Cross-Coupling Reactions
  作者：Sven S. Kampmann、Alexandre N. Sobolev、George A. Koutsantonis、Scott G. Stewart

  DOI：10.1002/adsc.201400201

  日期：2014.6.16

  phosphite‐based catalysts for use in the CN cross‐coupling reaction. The combination of nickel tetrakis(triphenyl phosphite) Ni[P(OPh)3]4} and 1,1′‐bis(diphenylphosphino)ferrocene (dppf), and in particular a newly developed catalyst (dppf)Ni[P(OPh)3]2, were found to be extremely effective in catalyzing a range of amination reactions of anilines and amines with aryl chlorides. This new catalyst system offers

  本文中，我们描述了用于CN交叉偶联反应的廉价，空气稳定的亚磷酸镍基催化剂的设计和制备。四（三亚磷酸三苯酯）镍Ni [P（OPh）3 ] 4 }和1,1'-双（二苯基膦基）二茂铁（dppf）的组合，尤其是新开发的催化剂（dppf）Ni [P（OPh） ）3 ] 2，被发现在催化一系列苯胺和胺与芳基氯化物的胺化反应中极为有效。这种新的催化剂体系提供了通常用于CN键形成的双（环辛二烯基）镍[Ni（COD）2 ]和钯（0）催化剂的替代品。
• The Synthesis and Catalytic Activity of New Mixed NHC-Phosphite Nickel(0) Complexes
  作者：Jeremy Duczynski、Alexandre N. Sobolev、Stephen A. Moggach、Reto Dorta、Scott G. Stewart

  DOI：10.1021/acs.organomet.9b00672

  日期：2020.1.13

  Herein we describe the synthesis and isolation of the first low-valent NHC-phosphite nickel complexes of general formula Ni(NHC)[P(OAr)3]2. These three-coordinate Ni(0) compounds were fully characterized, including by X-ray crystallography that highlighted their trigonal planar geometry. The representative complex Ni(IMes)[P(OPh)3]2 was used to show that a phosphite ligand is readily substituted in

  在这里，我们描述了通式Ni（NHC）[P（OAr）3 ] 2的第一批低价NHC-亚磷酸镍配合物的合成和分离。这些三坐标的Ni（0）化合物得到了充分的表征，包括通过X射线晶体学突出了它们的三角形平面几何形状。代表性络合物Ni（IMes）[P（OPh）3 ] 2“亚磷酸酯”用于表明亚磷酸酯配体在醛或腈的存在下容易被取代。这些化学计量的研究随后导致对它们在芳基甲苯磺酸盐和芳基硼酸之间的Suzuki-Miyaura交叉偶联反应中的催化性能的研究，这是此类NHC-Ni催化剂的首次应用。最后，机理研究导致分离出明确定义的氧化加成产物。
• An Air-Stable Nickel(0) Phosphite Precatalyst for Primary Alkylamine C-N Cross-Coupling Reactions
  作者：Sven S. Kampmann、Brian W. Skelton、Duncan A. Wild、George A. Koutsantonis、Scott G. Stewart

  DOI：10.1002/ejoc.201500734

  日期：2015.9

  preparation of a new air-stable nickel phosphite based catalyst for unique C–N bond forming processes. Specifically, (BINAP)Ni[P(OPh)3]2, is presented as an effective catalyst for a range of amination reactions between aryl halides and primary alkylamines. The results are supported by relevant kinetic studies, DFT calculations and a catalytic cycle indicating possible reaction intermediates.

  在本报告中，我们描述了一种用于独特 C-N 键形成过程的新型空气稳定亚磷酸镍基催化剂的设计和制备。具体而言，(BINAP)Ni[P(OPh)3]2 是芳基卤化物和伯烷基胺之间一系列胺化反应的有效催化剂。结果得到相关动力学研究、DFT 计算和指示可能的反应中间体的催化循环的支持。
• Organonickel(II) Complexes Containing Carbon-bonded Heterocycles as a Ligand
  作者：Kiyoshi Isobe、Yukio Nakamura、Shinichi Kawaguchi

  DOI：10.1246/bcsj.53.139

  日期：1980.1

  Oxidative addition reactions of 2- and 3-chloropyridines and of 2-chloropyrazine to tetrakis(triphenylphosphine)nickel(0) occurred in toluene at ambient temperature to afford dinuclear nickel(II) complexes containing carbon-bonded heterocycles as a ligand. They are quite stable and the bridging chloride was readily substituted by other halides and pseudohalides preserving the dinuclear structure. 8-Chloroquinoline

  2-和3-氯吡啶和2-氯吡嗪与四(三苯基膦)镍(0)在室温下在甲苯中发生氧化加成反应，得到含有碳键杂环作为配体的双核镍(II)配合物。它们非常稳定，桥接氯化物很容易被其他卤化物和拟卤化物取代，从而保持双核结构。作为例外，8-氯喹啉产生单核复合物。这些新型有机镍 (II) 配合物通过分析和分子量数据以及 IR、1H NMR 和 13C NMR 光谱进行表征。Di-μ-氯-双(2-吡啶基)双(三苯基膦)二镍(II)被发现是2-氯吡啶与甲基溴化镁选择性交叉偶联的优良催化剂。
• Preparation of Alkylnickel(II)–Phosphine Complexes by Reactions of Ni(acac)₂with Alkylaluminums in the Presence of Tertiary Phosphine
  作者：Takakazu Yamamoto、Masakatsu Takamatsu、Akio Yamamoto

  DOI：10.1246/bcsj.55.325

  日期：1982.1

  PR′3=triethylphosphine (PEt3), tributylphosphine (PBu3), 1,2-bis(diphenylphosphino)ethane(dpe)) and Ni(CH3)(acac)(PEtPh2) (PEtPh2=ethyldiphenylphosphine), have been prepared by reactions of Ni(acac)2 with AlR2(OC2H5) in the presence of phosphine ligands.

  四种新的烷基镍 (II)-膦配合物 NiR2(PR'3)2 (R=CH3, C2H5; PR'3=三乙基膦 (PEt3)、三丁基膦 (PBu3)、1,2-双(二苯基膦)乙烷(dpe) ) 和 Ni(CH3)(acac)(PEtPh2)（PEtPh2=乙基二苯基膦），已通过 Ni(acac)2 与 AlR2(OC2H5) 在膦配体存在下的反应制备。