四氯化钨 | 13470-13-8

• 物质功能分类: 无机化工 - 无机盐
• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 过渡金属盐
• 中文名称: 四氯化钨
• 中文别名: 氯化钨(IV)
• 英文名称: tungsten(IV) chloride
• 英文别名: tungsten tetrachloride；tetrachlorotungsten
• CAS: 13470-13-8
• 化学式: Cl₄W
• 分子量: 325.662
• InChiKey: YOUIDGQAIILFBW-UHFFFAOYSA-J

物化性质

• 熔点：
  decomposes [CRC10]
• 沸点：
  338.99°C (estimate)
• 密度：
  4,624 g/cm3
• 溶解度：
  与H2O反应
• 稳定性/保质期：
  其吸湿性不及五氯化钨，但遇水会水解。虽然加热不会使其熔融或升华，但在真空条件下于高温下分解，在水中也会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  2.76
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 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：
  C
• 安全说明：
  S26
• 危险类别码：
  R34
• 包装等级：
  III
• WGK Germany：
  3
• 危险品运输编号：
  UN 3260 8
• 储存条件：
  室温

SDS

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Section 1: Product Identification
Chemical Name: Tungsten (IV) chloride, 97%
CAS Registry Number: 13470-13-8
Formula: WCl4
EINECS Number: none
Chemical Family: metal halide
Synonym: Tungsten tetrachloride

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title Compound 13470-13-8 100% 1mg/m3 (as W - soluble) no data

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Section 3: Hazards Identification
Corrosive to skin and eyes. Material hydrolyzes in contact with moisture releasing toxic and corrosive fumes
Emergency Overview:
of hydrogen chloride and aqueous hydrochloric acid.
Primary Routes of Exposure: Contact with skin and eyes. Inhalation of dust.
Eye Contact: Corrosive irritant to the eyes.
Skin Contact: Corrosive to skin.
Inhalation: Forms hydrogen chloride in the presence of moisture. Inhalation can lead to burning of the respiratory tract.
Ingestion: No information is available on the acute physiological effects of ingestion.
Corrosive to skin, eyes and respiratory tract. Causes eye and skin burns, dyspnea (difficulty breathing) and
Acute Health Affects:
pulmonary edema.
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 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: not applicable
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: None. Material is non-flammable.
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 fumes of hydrogen chloride.
Decomposion Products:
Unusual Fire or Explosion Hazards: No unusual fire or explosion hazards.

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SECTION 6: Accidental Release Measures
Small spills can be mixed with powdered sodium bicarbonate, lime, or calcium carbonate and swept up. Avoid
Spill and Leak Procedures:
raising dust.

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SECTION 7: Handling and Storage
Store solid in a tightly sealed bottle away from moisture. If possible, handle solid in an efficient fume hood.
Handling and Storage:
Prolonged exposure to the atmosphere will lead to degradation of the product.

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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. Consult with glove manufacturer to determine the proper type of glove.
Ventilation: The solid may form corrosive vapors. It should be handled in an efficient fume hood.
If in form of fine dust and ventilation is not available a respirator should be worn. The use of respirators
Respirator:
requires a Respirator Protection Program to be in compliance with 29 CFR 1910.134.
Ventilation: The solid may form corrosive vapors. It should be handled in an efficient fume hood.
Additional Protection: No additional protection required.

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SECTION 9: Physical and Chemical Properties
Color and Form: gray pwdr.
Molecular Weight: 325.66
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: 4.624
Odor: pungent odor
Solubility in Water: reacts with water

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SECTION 10: Stability and Reactivity
Stability: moisture sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: contact with moisture
Incompatibility: active metals
Decomposition Products: Tungsten oxychloride, hydrogen 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 local, state and federal regulations.

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SECTION 14: Transportation
Shipping Name (CFR): Corrosive Solids, N.O.S.
Hazard Class (CFR): 8
Additional Hazard Class (CFR): NA
Packaging Group (CFR): II
UN ID Number (CFR): UN# 1759
Shipping Name (IATA): Corrosive Solid, N.O.S.
Hazard Class (IATA): 8
Additional Hazard Class (IATA): NA
Packaging Group (IATA): II
UN ID Number (IATA): UN# 1759

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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

制备方法与用途

合成制备方法

1. 在充入惰性气体的干燥箱中，将5g六氯化钨与聚四氟乙烯搅拌棒一起从图VI-9所示装置4处放入6中。随后熔封支管4，并用干冰冷却6处同时打开聚四氟乙烯旋塞从2抽气。采用减压蒸馏的方法，将精制脱水的四氯化碳引入6处至30mL。恢复常温后，抽真空并将6处浸入透明油浴中，使用500W灯泡照射，在150℃下反应3天。为确保安全，反应装置应围以防护屏。反应结束后冷却，将装置倒立通过玻璃过滤器3滤出产生的沉淀。若再次加热1处，由于有机溶剂回流，未反应的六氯化钨被萃取下来。萃取液成无色后停止加热，然后从2处抽气并打开聚四氟乙烯旋塞进行减压蒸馏，将有机溶剂完全逐出。在充入惰性气体的干燥箱中将6处切断取出玻璃过滤器上的生成物。该生成物含有五氯化钨等副产物杂质，在二氧化碳气流中加热时，六氯化钨中最易挥发的五氯化钨首先升华。再升高温度时，六氯化钨和二氯化钨也挥发出来，而四氯化钨不发生升华最终存留下来，收率为95%。

2. 在直径30mm的硼硅酸玻璃管中加入20～25g六氯化钨和计算量铝箔（使六氯化钨过量1～2g）。然后将反应管抽真空并封闭，在475℃下保温，装有六氯化钨的一端保持在225℃。约48小时后反应结束。此期间，生成的四氯化钨扩散至低温端并凝结为粗糙结晶状沉积物。为了去除过量六氯化钨和生成的氯化铝，在225℃下加热含有结晶粉末的一端，保持另一端在室温。随后在干燥箱中打开反应管取出四氯化钨。

反应信息

• 作为反应物：
  描述：

  四氯化钨 在 四氢呋喃 、 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 以86%的产率得到
  参考文献：
  名称：

  Schrock, Richard R.; Sturgeoff, Lynda G.; Sharp, Paul R., Inorganic Chemistry, 1983, vol. 22, # 20, p. 2801 - 2806

  摘要：

  DOI：
• 作为产物：
  描述：

  tungsten(IV) oxide 在 四氯化碳 作用下， 生成 四氯化钨
  参考文献：
  名称：

  Michael, A.; Murphey, A., American Chemical Journal, 1910, vol. 44, p. 382

  摘要：

  DOI：
• 作为试剂：
  描述：

  烯丙基腈 在 1,1,3,3-四甲基-1,3-二硅代环丁烷 、 四氯化钨 作用下， 以 苯 为溶剂， 60.0 ℃ 、1.33 Pa 条件下， 反应 10.0h， 生成 乙烯 、 1,4-二氰基-2-丁烯
  参考文献：
  名称：

  Metathesis of allyl cyanide in the presence of a catalytic system containing tungsten hexachloride and 1,1,3,3-tetramethyl-1,3-disilacyclobutane

  摘要：

  DOI：

  10.1007/bf01455511

文献信息

• COPPER NANOPARTICLE BASED CHEMOSELECTIVE REDUCTION
  申请人：Brown University

  公开号：US20210355073A1

  公开（公告）日：2021-11-18

  The instant invention provides processes for a chemo selective reduction of a nitro group within a compound in the presence of other groups which can also be reduced. This aspect of the present invention provides an ammonia borane (AB) initiated chemoselective reduction process of a nitro group contained within a compound in the presence of a copper (Cu) nanoparticle based catalyst. The invention is also directed to Copper (Cu) nanoparticle (NP) based catalysts, selected from Cu/WO x , Cu/SiO 2 , and Cu/C; wherein x represents an integer having a value of from about 2 to about 3.5, used in the chemo selective reduction of a nitro group contained within a compound in the presence of other groups which can also be reduced.

  该即时发明提供了一种在化合物中其他也可被还原的基团存在的情况下对硝基基团进行化学选择性还原的过程。本发明的这一方面提供了一种氨硼烷（AB）引发的化学选择性还原过程，用于在铜（Cu）纳米颗粒基催化剂存在的情况下对化合物中含有的硝基基团进行还原。该发明还涉及基于铜（Cu）纳米颗粒（NP）的催化剂，选自Cu/WOx、Cu/SiO2和Cu/C；其中x代表一个值约为2到3.5的整数，在化合物中其他也可被还原的基团存在的情况下用于对硝基基团进行化学选择性还原。
• α-Hydrogen migration reactions in tungsten(VI) cyclopentadienyl alkylidyne complexes
  作者：Timothy H. Warren、Richard R. Schrock、William M. Davis

  DOI：10.1016/s0022-328x(98)00781-5

  日期：1998.10

  CpW(CAd)(CH2CMe3)Cl and CpW(CAd)(CH2CMe3)2 tautomerize to give mixtures containing CpW(CCMe3)(CH2Ad)Cl and CpW(CCMe3)(CH2CMe3)(CH2Ad), respectively. An X-ray study of CpW(CAd)(CH2CMe3)2 is consistent with some α agostic interaction of a neopentyl proton in each neopentyl ligand with the metal. In contrast, CpW(CAd)(NMe2)(CH2CMe3) shows no evidence of tautomerizing to CpW(CCMe3)(NMe2)(CH2Ad) at room temperature over

  W（CAd）（OCMe 3）3（Ad = 1-金刚烷基）可以通过用1-金刚烷腈处理W 2（OCMe 3）6并转化为W（CAd）（三氟甲磺酸酯）（OCMe 3）2（dme）来制备通过用Me 3 Si（三氟甲磺酸酯）（dme = 1,2-二甲氧基乙烷）处理。W（CAd）（三氟甲磺酸酯）（OCMe 3）2（dme）与NaCp反应生成CpW（CAd）（OCMe 3）2。通过用Me 3 SiCl处理，可以在二氯甲烷中将CpW（CAd）（OCMe 3）2转化为CpW（CAd）Cl 2。CpW（CAd）Cl 2的烷基化产生CpW（CAd）（CH 2 CMe 3）Cl或CpW（CAd）R 2络合物（R = CH 2 CMe 3，CH 2 Ph或CH 3）。CpW（CAd）（CH 2 CMe 3）Cl和CpW（CAd）（CH 2 CMe 3）2均互变异构生成包含CpW（CCMe 3）（CH 2 Ad）Cl和CpW（CCMe
• AgPd Nanoparticles Deposited on WO_2.72 Nanorods as an Efficient Catalyst for One-Pot Conversion of Nitrophenol/Nitroacetophenone into Benzoxazole/Quinazoline
  作者：Chao Yu、Xuefeng Guo、Zheng Xi、Michelle Muzzio、Zhouyang Yin、Bo Shen、Junrui Li、Christopher T. Seto、Shouheng Sun

  DOI：10.1021/jacs.7b01983

  日期：2017.4.26

  acid, 2-nitrophenol, and aldehydes into benzoxazoles in near quantitative yields under mild conditions. The catalysis can also be extended to the one-pot reactions of ammonium formate, 2-nitroacetophenone, and aldehyde for high yield syntheses of quinazolines. Our studies demonstrate a new catalyst design to achieve a green chemistry approach to one-pot reactions for the syntheses of benzoxazoles and quinazolines

  我们报告了在 40 × 5 nm WO2.72 纳米棒 (NRs) 存在下 2.3 nm AgPd 纳米粒子 (NPs) 的种子介导生长，用于合成 AgPd/WO2.72 复合材料。AgPd NPs 和 WO2.72 NRs 之间的强相互作用使复合材料，尤其是 Ag48Pd52/WO2.72，对甲酸脱氢（TOF = 1718 h-1 和 Ea = 31 kJ/mol）和一锅反应具有催化活性在温和条件下以接近定量的产率将甲酸、2-硝基苯酚和醛转化为苯并恶唑。该催化作用还可以扩展到甲酸铵、2-硝基苯乙酮和醛的一锅反应，用于高产率合成喹唑啉。我们的研究展示了一种新的催化剂设计，可实现苯并恶唑和喹唑啉合成的一锅法反应的绿色化学方法。
• Low-temperature solid-state routes to transition metal oxides via metathesis reactions involving lithium oxide
  作者：A. Hector、I.P. Parkin

  DOI：10.1016/s0277-5387(00)81423-0

  日期：1993.8

  lithium oxide and anhydrous transition metal halide, MXn (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Cu, Zn, X = Cl; M = Mn, X = I), at oven temperatures of 450°C for 5 h produces crystalline transition metal oxide via a solid-state metathesis reaction. DSC studies show that the reaction is initiated at 300°C for M = Hf and Nb. When M = Ta or Nb the product is LiMO3. The metal oxides and lithium-metal

  摘要氧化锂和无水过渡金属卤化物MXn（M = Ti，Zr，Hf，V，Nb，Ta，Cr，Mo，W，Fe，Co，Ni，Cu，Zn，X = Cl; M = Mn，X = I），在450°C的烘箱温度下保持5 h，通过固态复分解反应生成结晶过渡金属氧化物。DSC研究表明，对于M ＝ Hf和Nb，反应在300℃开始。当M = Ta或Nb时，产物为LiMO3。通过X射线粉末衍射，SEM，EDAX，FT-IR和磁矩测量来表征金属氧化物和锂金属氧化物。
• The synthesis and characterization of α-Re2Cl4(depe)2 and α-W2Cl4(depe)2
  作者：Kathryn M. Carlson-Day、Judith L. Eglin、Kristi M. Huntington、Richard J. Staples

  DOI：10.1016/s0020-1693(97)05893-3

  日期：1998.4

  bidentate phosphine 1,2-bis(diethylphosphino)ethane, and α-W2Cl4(depe)2 allows the comparison of the crystallographic and spectroscopic properties of these two new compounds. Characterization methods for α-Re2Cl4(depe)2 and α-W2Cl4(depe)2 include 31P1H NMR spectroscopy, UV-Vis spectroscopy and X-ray crystallography. In addition to α-W2Cl4(depe)2, both cationic and anionic tungsten complexes without metal-metal

  合成两个α-Re的2氯4（DEPE）2，其中DEPE是二齿膦1,2-二（二乙基膦基）乙烷，和α-W 2氯4（DEPE）2允许晶体和光谱的比较这两种新化合物的性质。对于α-Re的表征方法2氯4（DEPE）2和α-W 2氯4（DEPE）2包括31 P 1 H NMR光谱，UV-Vis光谱和X-射线晶体学。除了α-W 2氯4（DEPE）2，没有金属-金属键合的阳离子和阴离子钨配合物均被分离并进行结构表征。用于晶体学数据α-Re的2氯4（DEPE）2，α-W 2氯4（DEPE）2和[WOCL（DEPE）2 ] 2 [WOCL 4（OP（CH 2 CH 3）2 CH 2）2 ]如下：P 2 1 / c（No. 14）其中，wR 2 = 0.0875；C 2 / c（第15号），带有和wR 2 = 0.0948;和P 2 1 / n（No. 14）与。ž = 4，- [R 1 = 0.0522和WR 2