[bis(tributylphosphine)nickeldichloride] | 15274-43-8

• 物质功能分类: 催化剂及助剂 - 偶联剂
• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: [bis(tributylphosphine)nickeldichloride]
• 英文别名: NiCl2(P-n-Bu3)2；NiCl2(tri-n-butylphosphine)2；Ni(PⁿBu₃)₂Cl₂；(n-Bu₃P)₂NiCl₂ ；NiCl2(PBu3)2；(P(n-Bu)₃)₂NiCl₂；[NiCl₂(nBu₃P)₂]；Ni(nBu₃P)₂Cl₂；(Bu3P)2 nickel(II)Cl2；NiCl2(P(Bu(n))3)2；[NiCl2(P(n-butyl)3)2]；nickel(2+);tributylphosphane;dichloride
• CAS: 15274-43-8
• 化学式: C₂₄H₅₄Cl₂NiP₂
• 分子量: 534.236
• InChiKey: KPFOFXWYYUNJOZ-UHFFFAOYSA-L

物化性质

• 熔点：
  43-45 °C (lit.)

计算性质

• 辛醇/水分配系数(LogP)：
  11.11
• 重原子数：
  29
• 可旋转键数：
  18
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 危险等级：
  8
• 危险品标志：
  T
• 安全说明：
  S53
• 危险类别码：
  R45
• WGK Germany：
  3
• 危险品运输编号：
  UN 1759 8
• 包装等级：
  III
• 危险类别：
  8
• 危险性防范说明：
  P201,P261,P280,P305+P351+P338,P310
• 危险性描述：
  H302,H312,H314,H317,H332,H334,H350
• 储存条件：
  贮存于阴凉处，并保持容器密封，在干燥、通风良好的环境中存放。

SDS

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Section 1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product identifiers
Product name : Dichlorobis(tributylphosphine)nickel(II)
CAS-No. : 15274-43-8
Relevant identified uses of the substance or mixture and uses advised against
Identified uses : Laboratory chemicals, Manufacture of substances

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Section 2. HAZARDS IDENTIFICATION
Classification of the substance or mixture
Classification according to Regulation (EC) No 1272/2008 [EU-GHS/CLP]
Acute toxicity, Inhalation (Category 4)
Acute toxicity, Dermal (Category 4)
Acute toxicity, Oral (Category 4)
Skin corrosion (Category 1B)
Serious eye damage (Category 1)
Respiratory sensitization (Category 1)
Skin sensitization (Category 1)
Carcinogenicity (Category 1B)
Classification according to EU Directives 67/548/EEC or 1999/45/EC
May cause cancer. Harmful by inhalation, in contact with skin and if swallowed. Causes burns. May cause
sensitization by inhalation and skin contact.
Label elements
Labelling according Regulation (EC) No 1272/2008 [CLP]
Pictogram
Signal word Danger
Hazard statement(s)
H302 Harmful if swallowed.
H312 Harmful in contact with skin.
H314 Causes severe skin burns and eye damage.
H317 May cause an allergic skin reaction.
H332 Harmful if inhaled.
H334 May cause allergy or asthma symptoms or breathing difficulties if inhaled.
H350 May cause cancer.
Precautionary statement(s)
P201 Obtain special instructions before use.
P261 Avoid breathing dust.
P280 Wear protective gloves/ protective clothing/ eye protection/ face
protection.
P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove
contact lenses, if present and easy to do. Continue rinsing.
P310 Immediately call a POISON CENTER or doctor/ physician.
Supplemental Hazard none
Statements
Restricted to professional users.
According to European Directive 67/548/EEC as amended.
Hazard symbol(s)
R-phrase(s)
R45 May cause cancer.
R20/21/22 Also harmful by inhalation, in contact with skin and if swallowed.
R34 Causes burns.
R42/43 May cause sensitization by inhalation and skin contact.
S-phrase(s)
S53 Avoid exposure - obtain special instructions before use.
S22 Do not breathe dust.
S26 In case of contact with eyes, rinse immediately with plenty of water and
seek medical advice.
S27 Take off immediately all contaminated clothing.
S28 After contact with skin, wash immediately with plenty of water.
S36/37/39 Wear suitable protective clothing, gloves and eye/face protection.
S45 In case of accident or if you feel unwell, seek medical advice immediately
(show the label where possible).
Restricted to professional users.
Other hazards - none

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Section 3. COMPOSITION/INFORMATION ON INGREDIENTS
Substances
Formula : C24H54Cl2NiP2
Molecular Weight : 534,23 g/mol
Component Concentration
Dichlorobis(tributylphosphine)nickel(II)
CAS-No. 15274-43-8 -

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Section 4. FIRST AID MEASURES
Description of first aid measures
General advice
Consult a physician. Show this safety data sheet to the doctor in attendance.
If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.
In case of skin contact
Take off contaminated clothing and shoes immediately. Wash off with soap and plenty of water. Consult a
physician.
In case of eye contact
Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.
If swallowed
Do NOT induce vomiting. Never give anything by mouth to an unconscious person. Rinse mouth with
water. Consult a physician.
Most important symptoms and effects, both acute and delayed
Material is extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes, and
skin., spasm, inflammation and edema of the larynx, spasm, inflammation and edema of the bronchi,
pneumonitis, pulmonary edema, burning sensation, Cough, wheezing, laryngitis, Shortness of breath,
Headache, Nausea
Indication of any immediate medical attention and special treatment needed
no data available

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Section 5. FIREFIGHTING MEASURES
Extinguishing media
Suitable extinguishing media
Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.
Special hazards arising from the substance or mixture
Carbon oxides, Oxides of phosphorus, Hydrogen chloride gas, Nickel/nickel oxides
Advice for firefighters
Wear self contained breathing apparatus for fire fighting if necessary.
Further information
no data available

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Section 6. ACCIDENTAL RELEASE MEASURES
Personal precautions, protective equipment and emergency procedures
Use personal protective equipment. Avoid dust formation. Avoid breathing vapors, mist or gas. Ensure
adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust.
Environmental precautions
Prevent further leakage or spillage if safe to do so. Do not let product enter drains.
Methods and materials for containment and cleaning up
Pick up and arrange disposal without creating dust. Sweep up and shovel. Keep in suitable, closed
containers for disposal.
Reference to other sections
For disposal see section 13.

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Section 7. HANDLING AND STORAGE
Precautions for safe handling
Avoid contact with skin and eyes. Avoid formation of dust and aerosols.Avoid exposure - obtain special
instructions before use.
Provide appropriate exhaust ventilation at places where dust is formed.
Conditions for safe storage, including any incompatibilities
Store in cool place. Keep container tightly closed in a dry and well-ventilated place.
Recommended storage temperature: 2 - 8 °C
Specific end use(s)
no data available

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Section 8. EXPOSURE CONTROLS/PERSONAL PROTECTION
Control parameters
Components with workplace control parameters
Exposure controls
Appropriate engineering controls
Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and
at the end of workday.
Personal protective equipment
Eye/face protection
Face shield and safety glasses Use equipment for eye protection tested and approved under
appropriate government standards such as NIOSH (US) or EN 166(EU).
Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique
(without touching glove's outer surface) to avoid skin contact with this product. Dispose of
contaminated gloves after use in accordance with applicable laws and good laboratory practices.
Wash and dry hands.
The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and
the standard EN 374 derived from it.
Body Protection
Complete suit protecting against chemicals, The type of protective equipment must be selected
according to the concentration and amount of the dangerous substance at the specific workplace.
Respiratory protection
Where risk assessment shows air-purifying respirators are appropriate use a full-face particle
respirator type N100 (US) or type P3 (EN 143) respirator cartridges as a backup to engineering
controls. If the respirator is the sole means of protection, use a full-face supplied air respirator. Use
respirators and components tested and approved under appropriate government standards such
as NIOSH (US) or CEN (EU).

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Section 9. PHYSICAL AND CHEMICAL PROPERTIES
Information on basic physical and chemical properties
a) Appearance Form: powder
Colour: red
b) Odour no data available
c) Odour Threshold no data available
d) pH no data available
e) Melting point/freezing Melting point/range: 43 - 45 °C - lit.
point
f) Initial boiling point and no data available
boiling range
g) Flash point no data available
h) Evaporation rate no data available
i) Flammability (solid, gas) no data available
j) Upper/lower no data available
flammability or
explosive limits
k) Vapour pressure no data available
l) Vapour density no data available
m) Relative density no data available
n) Water solubility no data available
o) Partition coefficient: n- no data available
octanol/water
p) Auto-ignition no data available
temperature
q) Decomposition no data available
temperature
r) Viscosity no data available
s) Explosive properties no data available
t) Oxidizing properties no data available
Other safety information
no data available

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Section 10. STABILITY AND REACTIVITY
Reactivity
no data available
Chemical stability
no data available
Possibility of hazardous reactions
no data available
Conditions to avoid
no data available
Incompatible materials
Strong oxidizing agents
Hazardous decomposition products
Other decomposition products - no data available

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Section 11. TOXICOLOGICAL INFORMATION
Information on toxicological effects
Acute toxicity
no data available
Skin corrosion/irritation
no data available
Serious eye damage/eye irritation
no data available
Respiratory or skin sensitization
no data available
Germ cell mutagenicity
no data available
Carcinogenicity
Possible human carcinogen
IARC: No component of this product present at levels greater than or equal to 0.1% is identified as
probable, possible or confirmed human carcinogen by IARC.
Reproductive toxicity
no data available
Specific target organ toxicity - single exposure
no data available
Specific target organ toxicity - repeated exposure
no data available
Aspiration hazard
no data available
Potential health effects
Inhalation Harmful if inhaled. Material is extremely destructive to the tissue of the
mucous membranes and upper respiratory tract.
Ingestion Harmful if swallowed. Causes burns.
Skin Harmful if absorbed through skin. Causes skin burns.
Eyes Causes eye burns.
Signs and Symptoms of Exposure
Material is extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes, and
skin., spasm, inflammation and edema of the larynx, spasm, inflammation and edema of the bronchi,
pneumonitis, pulmonary edema, burning sensation, Cough, wheezing, laryngitis, Shortness of breath,
Headache, Nausea
Additional Information
RTECS: Not available

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Section 12. ECOLOGICAL INFORMATION
Toxicity
no data available
Persistence and degradability
no data available
Bioaccumulative potential
no data available
Mobility in soil
no data available
Results of PBT and vPvB assessment
no data available
Other adverse effects
no data available

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Section 13. DISPOSAL CONSIDERATIONS
Waste treatment methods
Product
Offer surplus and non-recyclable solutions to a licensed disposal company. Dissolve or mix the material
with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber.
Contaminated packaging
Dispose of as unused product.

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Section 14. TRANSPORT INFORMATION
UN number
ADR/RID: 1759 IMDG: 1759 IATA: 1759
UN proper shipping name
ADR/RID: CORROSIVE SOLID, N.O.S. (Dichlorobis(tributylphosphine)nickel(II))
IMDG: CORROSIVE SOLID, N.O.S. (Dichlorobis(tributylphosphine)nickel(II))
IATA: Corrosive solid, n.o.s. (Dichlorobis(tributylphosphine)nickel(II))
Transport hazard class(es)
ADR/RID: 8 IMDG: 8 IATA: 8
Packaging group
ADR/RID: II IMDG: II IATA: II
Environmental hazards
ADR/RID: no IMDG Marine Pollutant: no IATA: no
Special precautions for user
no data available

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Section 15. REGULATORY INFORMATION
This safety datasheet complies with the requirements of Regulation (EC) No. 1907/2006.
Safety, health and environmental regulations/legislation specific for the substance or mixture
no data available
Chemical Safety Assessment
no data available

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Section 16. OTHER INFORMATION
Further information
Copyright 2012 Co. LLC. License granted to make unlimited paper copies for internal use
only.
The above information is believed to be correct but does not purport to be all inclusive and shall be
used only as a guide. The information in this document is based on the present state of our knowledge
and is applicable to the product with regard to appropriate safety precautions. It does not represent any
guarantee of the properties of the product. Corporation and its Affiliates shall not be held
liable for any damage resulting from handling or from contact with the above product. See
and/or the reverse side of invoice or packing slip for additional terms and conditions of sale.

制备方法与用途

二氯二(三丁基膦)镍(II)是一种金属催化剂，广泛应用于各种偶联反应中，例如将乙烯二聚生成丁烯，进而用于生产维拉佐酮及其中间体。

反应信息

• 作为反应物：
  描述：

  [bis(tributylphosphine)nickeldichloride] 在 sodium 作用下， 以 xylene 为溶剂， 生成 Ni(PBu3)4
  参考文献：
  名称：

  Electrochemical reduction of Ni(II) phosphine and phosphite complexes

  摘要：

  DOI：

  10.1007/bf00949160
• 作为产物：
  描述：

  {(Cl-P=CTMS2)Ni(PBu3)2} 生成 [bis(tributylphosphine)nickeldichloride]
  参考文献：
  名称：

  反应P η：β-卤代磷烯烃镍和铂的烯烃络合物2 -CO-协调和不寻常的氧化加成行为

  摘要：

  磷烯烃X–P CTMS 2（X = F，Cl，l; TMS = SiMe 3）对金属络合物（Bu 3 P）2 Ni（cod）（cod =环-octa-1,5- ）显示不同的反应行为二烯）或（PH 3 P）2铂（C 2 H ^ 4），分别进行任一配合，得到η 2 ;磷烯烃络合物或替代地氧化加成的P-X键，形成磷烯基-金属（II）配合物，[（R 3 P）2 M（X）（σ- PCTMS 2）]。

  DOI：

  10.1039/c39890001206
• 作为试剂：
  描述：

  2-甲氧基联苯 、 苯基溴化镁 在 [bis(tributylphosphine)nickeldichloride] 作用下， 以 2-甲基四氢呋喃 、 乙醚 为溶剂， 反应 16.0h， 以86%的产率得到邻三联苯
  参考文献：
  名称：

  受阻较少的配体为镍催化芳族醚的格利雅交联提供了改进的催化剂†

  摘要：

  已经发现，使用空间位阻较少的配体的镍配合物可以最有效地催化未活化的邻位取代的芳族醚与格氏试剂的挑战性反应。空气稳定，廉价，可商购的[NiCl 2（P n Bu 3）2 ]是这类转化的改进催化剂。当在更高的温度和低至0.1摩尔％的催化剂负载下进行检查时，这种催化剂的改进结果甚至可以扩展到活化程度更高的底物的某些偶联。在后面这些反应中异常的诱导期与充当助催化剂的副产物镁盐有关。

  DOI：

  10.1039/c7cy01205e

文献信息

• Coordination chemistry of higher oxidation states Part 9 [1]. Nickel(III) complexes of monodentate phosphines and related ligands
  作者：Simon J. Higgins、William Levason、Deborah J. Wilkes

  DOI：10.1016/s0020-1693(00)87660-4

  日期：1984.4

  The known nickel(III) complexes [Ni(PR3)2X3]) (X = Cl, Br) with monodentate phosphines (PMe3, PEt3, PnBu3, PMe2Ph X = Br only) have been reexamined, some being obtaines in a pure state for the first time. New complexes with PMe2Ph, PEt2Ph and PMePh2 are described. Detailed spectroscopic data (IR, UV/Visible and EPR) are reported and assigned for all complexes, leading to the proposal of trans-trigonal

  已知镍（III）配合物[镍（PR 3）2 X 3 ]）（X =氯，溴）与单齿膦（PME 3， PET 3，P Ñ卜3，PME 2博士X只为Br）已经重新审查，有些是第一次获得纯净状态。与PME新复合物2 PH，PET 2 h和PMePh 2描述。报告了所有配合物的详细光谱数据（IR，UV / Visible和EPR）并进行了分配，从而提出了跨三角双锥体结构（D 3h）的建议，以证明P（OMe）的镍（III）配合物在溶液中形成）3，AsEt 3，PCy 3（Cy =环己基），PPh 3也被给出。讨论了影响这些配合物稳定性的因素。
• Darstellung und struktur von hetero- und homoleptischen thiomethylnickelkomplexen
  作者：Frank Becke、Tobias Rüffer、Roland Boese、Dieter Bläser、Dirk Steinborn

  DOI：10.1016/s0022-328x(97)00190-3

  日期：1997.1

  Thiomethyl nickel complexes [Ni(CH2SR)2(PBu3)2] (R = Me (1a), ’Bu (1b), Ph (1e)) and the homoleptic derivatives [Li(Et2O)}2Ni(CH2S’Bu)4] (2), [Li2Ni(CH2SMe)4] · x thf (3a) and [Li2Ni(CH2SPh)4] · x Et2O (3b) were synthesized by the reaction of nickel halide phosphine complexes with the appropriate thiomethyl lithium compounds LiCH2SR in a molar ratio of 1/2 and 1/4, respectively. The molecular structures

  硫代甲基镍络合物[Ni（CH 2 SR）2（PBu 3）2 ]（R = Me（1a），'Bu（1b），Ph（1e））和均配衍生物[Li（Et 2 O）} 2 Ni（CH 2 S'Bu）4 ]（2），[Li 2 Ni（CH 2 SMe）4 ]· x thf（3a）和[Li 2 Ni（CH 2 SPh）4 ]· x Et 2 O（3b）通过卤化镍膦配合物与合适的硫代甲基锂化合物LiCH 2 SR的摩尔比分别为1/2和1/4的反应合成）。反磁性杂配体衍生物1的分子结构（X射线）显示出具有正方形平面的NiC 2 P 2单元的C 1对称性。配体以转位方式排列。配合物1通过微量分析和NMR光谱来表征。的叔-butylthiomethyl复杂2是在室温下稳定（Ť癸〜60–66°C），而甲基和苯基硫代甲基络合物3a和3b已在-10至-20°C时分解。配合物2的分子结构（X射线）显示四个亚甲基碳原子和镍的平面排列略有扭曲（d（Ni-C）=
• Small Phosphine Ligands Enable Selective Oxidative Addition of Ar–O over Ar–Cl Bonds at Nickel(0)
  作者：Emily D. Entz、John E. A. Russell、Leidy V. Hooker、Sharon R. Neufeldt

  DOI：10.1021/jacs.0c06995

  日期：2020.9.9

  aryl chlorides. This is because Ni(0) and Pd(0) often undergo oxidative addition of organohalides at a similar or faster rate than most Ar-O bonds. DFT and stoichiometric oxidative addition studies demonstrate that small phosphines, in particular PMe3, are unique in promoting preferential reaction of Ni(0) with aryl tosylates and other C-O bonds in the presence of aryl chlorides. This selectivity was

  非三氟甲磺酸酯苯酚衍生物的 Suzuki-Miyaura 偶联的当前方法受限于它们对卤化物（包括芳基氯）的不耐受性。这是因为 Ni(0) 和 Pd(0) 通常以与大多数 Ar-O 键相似或更快的速率进行有机卤化物的氧化加成。DFT 和化学计量氧化加成研究表明，小膦，特别是 PMe3，在促进 Ni(0) 与芳基甲苯磺酸酯和其他 CO 键在芳基氯化物存在下的优先反应方面是独一无二的。这种选择性在第一个 Ni 催化的 CO 选择性 Suzuki-Miyaura 偶联氯化苯酚衍生物中得到了利用，其中含氧离去基团不是氟化磺酸盐，例如三氟甲磺酸盐。计算研究表明，PMe3 和其他膦之间发散选择性的起源不同于配体控制的化学发散交叉偶联的先前例子。由于电子和空间因素，PMe3 影响甲苯磺酸盐的选择性反应。在氧化加成过程中镍和甲苯磺酸的磺酰氧之间的密切相互作用对观察到的选择性至关重要。
• Homogeneous catalysis of the water gas shift reaction by NiX2-tertiary phosphine systems
  作者：Potenzo Giannoccaro、Emiliano Pannacciulli、Giuseppe Vasapollo

  DOI：10.1016/s0020-1693(00)87578-7

  日期：1985.1

  NiX2L2 (X = Cl, Br; L = PMe3 PEt3 PBut3, P(i-Pr)3, PMe2Ph, PEt2Ph) aqueous-alcoholic solutions, catalyze the water gas shift reaction (W.G.S.R.) under carbon monoxide at atmospheric pressure and temperatures higher than 90 °C. The catalysis is accomplished through the following main reactions: NiX2L2 + 3CO + H2O → Ni(CO)2L2 + 2HX + CO2; Ni(CO)2L2 + 2HX → NiX2L2 + H2, which can also be carried out separately

  所述NIX 2大号2（X =氯，溴; L = PME 3 PET 3 PBut 3，P（I-PR）3，PME 2 PH，PET 2 PH）水-醇溶液，催化水煤气变换反应（WGSR ），一氧化碳，大气压和高于90°C的温度。该催化作用通过以下主要反应完成：NiX 2 L 2 + 3CO + H 2 O→Ni（CO）2 L 2 + 2HX + CO 2；Ni（CO）2 L 2 + 2HX + CO 2；Ni（CO）2 L 2 + 2HX + CO 2。Ni（CO）2 L 2 + 2HX→NiX 2 L 2 + H2，也可以单独进行。催化活性随时间缓慢降低，顺序为：PR 3
• CFC replacement HCFC-133a (CF3CH2Cl) as a convenient precursor for the synthesis of chlorodifluorovinyl-metal derivatives of main group and transition metal elements: the first X-ray structural characterisation of chlorodifluorovinyl-containing organometallic complexes
  作者：Nicholas A Barnes、Alan K Brisdon、Wendy I Cross、Joseph G Fay、Jacqueline A Greenall、Robin G Pritchard、James Sherrington

  DOI：10.1016/s0022-328x(00)00565-9

  日期：2000.12

  The one-pot reaction of the CFC replacement 1-chloro-2,2,2-trifluoroethane (CF3CH2Cl, HCFC-133a) with two equivalents of butyllithium in diethylether at −78°C followed by the addition of main group or transition metal halides results in good yields of the metal-chlorodifluorovinyl-containing compounds R3Sn(CClCF2) R=Me, Et, Bu}, Sn(CClCF2)4, Sb(CClCF2)3, Hg(CClCF2)nCl(2−n) (n=1,2), trans-[Ni(CClCF2)2(PBu3)2]

  在-78°C下，将CFC取代的1-氯-2,2,2-三氟乙烷（CF 3 CH 2 Cl，HCFC-133a）与二当量的丁基锂在乙醚中进行一锅反应，然后添加主基或过渡金属卤化物导致含金属chlorodifluorovinyl-化合物中，R的良好产率3 SN（CClCF 2）R =甲基，乙基，卜}，锡（CClCF 2）4，锑（CClCF 2）3，Hg（上CClCF 2）ñ氯（2- ñ）（ñ = 1,2），反式- [镍（CClCF 2）2（PBU 3）2 ]，反式-[Pd（CCl 3 CF 2）2（PBu 3）2 ]和[Au（CCl 3 CF 2）（PPh 3）]。汞柱（CClCF的分子结构2）氯，反式- [钯（CClCF 2）2（BU 3 P）2 ]和[金（CClCF 2）（PPH 3）]已从单一获得水晶数据 这些是关于任何含氯二氟乙烯基的有机金属配合物的第一个此类结构数据。的[AU（CFCF分子结构2）（PPH