Tris(t-butoxy)(2,2-dimethylpropylidyne)tungsten(VI), 98% Schrock Alkyne Metathesis Catalyst | 78234-36-3

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: Tris(t-butoxy)(2,2-dimethylpropylidyne)tungsten(VI), 98% Schrock Alkyne Metathesis Catalyst
• 英文别名: tris(2-methyl-2-propoxy)(2,2-dimethylpropylidyne)tungsten(VI)；tris(tert-butoxy)(2,2-dimethylpropylidyne)tungsten(VI)；tri-tert-butoxy(2,2-dimethylpropylidyne)tungsten；tris(t-butoxy)(2,2-dimethylpropylidyne)tungsten；Schrock's tungsten catalyst；Schrock's carbyne catalyst
• CAS: 78234-36-3
• 化学式: C₁₇H₃₆O₃W
• 分子量: 472.321
• InChiKey: OSPGYWVJGVLTDI-UHFFFAOYSA-N

物化性质

• 稳定性/保质期：

  遵照规定使用和储存，则不会发生分解。

计算性质

• 辛醇/水分配系数(LogP)：
  5.34
• 重原子数：
  21.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

安全信息

• 安全说明：
  S26,S36/37/39
• 危险类别码：
  R36/37/38
• 海关编码：
  2909199090
• 储存条件：
  存放于阴凉干燥处。

SDS

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Section 1: Product Identification
Chemical Name: Tris(t-butoxy)(2,2-dimethylpropylidyne)tungsten (VI), 98% Schrock Alkyne Metathesis Catalyst
CAS Registry Number: 78234-36-3
Formula: (C4H9O)3W?CC(CH3)3
EINECS Number: none
Chemical Family: Metal akylidyne
Synonym: Schrock Alkyne Metathesis Catalyst; Tris(tert-butanolato)(2,2-dimethylpropylidyne)tungsten

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 78234-36-3 100% 5mg/m3 (as W) no data

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin, eyes and respiratory tract.
Primary Routes of Exposure: Inhalation, skin, eyes
Eye Contact: Causes slight to mild irritation of the eyes.
Skin Contact: Causes slight to mild irritation of the skin.
Inhalation: Causes irritation to the nose, mucous membranes and respiratory tract.
Ingestion: No specific information is available on the physiological effects of ingestion.
Acute Health Affects: Irritating to skin, eyes and respiratory tract.
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 soap and water. Remove contaminated clothes if necessary. Seek medical
Skin Exposure:
assistance if 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 involved in a fire, fire fighters should be equipped with a NIOSH approved positive pressure self-contained
Special Fire Fighting Procedures:
breathing apparatus and full protective clothing.
Hazardous Combustion and If involved in a fire material may release toxic and irritating 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: Material is air and moisture sensitive. Store cold and handle under an inert atmosphere of nitrogen or argon.

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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: If possible, handle the material in an efficient fume hood.
If ventilation is not available, a respirator should be worn. The use of respirators requires a Respiratory
Respirator:
Protection Program to be in compliance with 29 CFR 1910.134.
Ventilation: If possible, 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: off-white to tan powder
Molecular Weight: 472.31
Melting Point: no data
Boiling Point: no data
Vapor Pressure: 0.000001mm Hg (50°)
Specific Gravity: no data
Odor: none
Solubility in Water: insoluble

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SECTION 10: Stability and Reactivity
Stability: air sensitive, moisture sensitive (store cold)
Hazardous Polymerization: No hazardous polymerization
Conditions to Avoid: air and moisture
Strong oxidizing agents, alcohols, water, carboxylic and mineral acids, peroxides, chlorinated solvents,
Incompatibility:
halogens
Decomposition Products: Carbon monoxide, tungsten oxide, hydrogen and water

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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 federal, state and local 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：

  Tris(t-butoxy)(2,2-dimethylpropylidyne)tungsten(VI), 98% Schrock Alkyne Metathesis Catalyst 在 溶剂黄146 作用下， 以 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Freudenberger, John H.; Schrock, Richard R., Organometallics, 1985, vol. 4, # 11, p. 1937 - 1944

  摘要：

  DOI：
• 作为产物：
  描述：

  di-tert-butoxybis(4-chlorophenoxy)(2,2-dimethylpropylidene)tungsten 、 lithium tert-butoxide 以 not given 为溶剂， 生成 Tris(t-butoxy)(2,2-dimethylpropylidyne)tungsten(VI), 98% Schrock Alkyne Metathesis Catalyst
  参考文献：
  名称：

  Freudenberger, John H.; Schrock, Richard R., Organometallics, 1985, vol. 4, # 11, p. 1937 - 1944

  摘要：

  DOI：
• 作为试剂：
  描述：

  1-甲基-4-苯基乙炔苯 在 Tris(t-butoxy)(2,2-dimethylpropylidyne)tungsten(VI), 98% Schrock Alkyne Metathesis Catalyst 作用下， 以 甲苯 为溶剂， 生成 2,2,5,5-四甲基-3-己炔 、 (3,3-二甲基-1-丁炔)-苯 、 1-(3,3-二甲基丁-1-炔基)-4-甲基苯
  参考文献：
  名称：

  Metathesis of acetylenes by tungsten(VI)-alkylidyne complexes

  摘要：

  DOI：

  10.1021/ja00403a058

文献信息

• Total Synthesis of Myxovirescin A1
  作者：Alois Fürstner、Melanie Bonnekessel、Jarred T. Blank、Karin Radkowski、Günter Seidel、Fabrice Lacombe、Barbara Gabor、Richard Mynott

  DOI：10.1002/chem.200700926

  日期：2007.10.26

  exquisitely selective ring closing alkyne metathesis reaction (RCAM) catalyzed by the molybdenum tris-amido complex 20 activated in situ with CH2Cl2. The resulting cyclic enyne 76 was subjected to a ruthenium catalyzed trans-hydrosilylation/proto-desilylation tandem. Although [Cp*Ru(MeCN)3]PF6 had previously been recommended as catalyst of choice for trans-hydrosilylation reactions of internal alkynes

  描述了大环内酯类抗生素大霉素Myxovirescin A1（1）的收敛性总合成，该合成主要基于试剂和催化剂控制的转化。这包括二溴代烯烃48与炔基锌试剂的高度区域选择性Negishi反应，以及所得烯炔衍生物12与衍生自烯烃61的9-BBN加合物的钯催化烷基-铃木偶联。氢化β-酮酸酯49和功能化醛53的抗选择性氧化烯丙基化是关键步骤。然而，在氧化烯丙基化步骤中使用的双硼化烯丙基供体57的制备需要进行仔细的优化，并导致对经典的硼氢化剂“二（异硫代樟脑基）硼烷（Ipc2BH）”的性质有重要的认识。X射线晶体学清楚地表明，该化合物为固态二聚体，但当溶于CH2Cl2或苯中时，则容易发生基本上定量的单脱硼化作用。从11B NMR数据可以看出，它在醚溶剂中的组成甚至更加复杂。将衍生自12和61的产物71精制为烯炔-炔衍生物75，该烯炔用作通过用 原位活化的三氨基合钼络合物20催化的精细选择性闭环
• Synthesis and Characterization of Tungsten Alkylidene and Alkylidyne Complexes Featuring a New Carbazole-Based Rigid Trianionic ONO^3– Pincer-Type Ligand
  作者：Ushnish Mandal、Sudarsan VenkatRamani、Ion Ghiviriga、Khalil A. Abboud、Adam S. Veige

  DOI：10.1021/acs.organomet.0c00150

  日期：2020.6.22

  of a rigid carbazole trianionic pincer ligand and its tungsten alkylidene [CBZ-ONO]W═CHtBu(OtBu) (3) and anionic alkylidyne Ph3PCH3}[CBZ-ONO]W≡CtBu(OtBu)} (4) complexes are reported. Designed to maximize the inorganic enamine effect by constraining the N atom lone pair, the carbazole ligand achieves high planarity. However, the orbital overlap remains similar to that of the flexible ligand [CF3–ONO]H3

  刚性咔唑三阴离子钳配体的设计和合成及其钨亚烷基[CBZ-ONO]W═CH吨卜（O吨卜）（3）和阴离子次烷基博士3 PCH 3 } [CBZ-ONO]W≡报道了C t Bu（O t Bu）}（4）络合物。通过限制N原子孤对来最大程度地发挥无机烯胺作用，咔唑配体具有很高的平面度。但是，轨道重叠仍然与柔性配体[CF 3 –ONO] H 3（1）。无法合成中性亚烷基复合物。通过多核NMR光谱，燃烧分析，质谱和单晶X射线衍射对复合物进行表征。DFT计算显示出带有刚性和柔性配体的亚烷基配合物中的无机烯胺轨道重叠。
• Unusually stable tungstenacyclobutadienes featuring an ONO trianionic pincer-type ligand
  作者：Matthew E. O'Reilly、Ion Ghiviriga、Khalil A. Abboud、Adam S. Veige

  DOI：10.1039/c2dt32653a

  日期：——

  tungsten alkylidyne complex, [CF3–ONO]WC(tBu)(OEt2) (5) where CF3–ONO = (MeC6H3[C(CF3)2O])2N3−}. Treating 5 with 1-phenylpropyne, 4,4-dimethyl-2-pentyne, and cyclooctyne yields the corresponding tungstenacyclobutadiene complexes [CF3–ONO]W[κ2-C(tBu)C(Me)C(Ph)] (6), [CF3–ONO]W[κ2-C(tBu)C(Me)C(tBu)] (7), and [CF3–ONO]W[κ2-C(tBu)C(CH2)6C] (8). Complexes 6, 7, and 8 do not undergo retro-[2 + 2]-cycloaddition

  本报告介绍了第一个中性三阴离子ONO钳型钨亚烷基络合物[CF 3 –ONO] W C（t Bu）（OEt 2）（5）其中CF 3 –ONO =（MeC 6 H 3 [ C（CF 3）2 O]）2 N 3− }。用5处理1-苯基丙炔， 4,4-二甲基-2-戊炔， 和 环辛炔得到相应的tungstenacyclobutadiene络合物[CF 3 -ONO] W [κ 2 -C（吨卜）C（Me）的C（PH）]（6），[CF 3 -ONO] W [κ 2 -C（吨丁基） C（Me）的C（吨丁基）]（7），和[CF 3 -ONO] W [κ 2 -C（吨卜）C（CH 2）6 C]（8）。配合物6，7和8不即使在200℃或在PME的存在下经历后向[2 + 2] -环3。DFT方法阐明络合物的电子结构图5和图6揭示了重要的电子因素，其导致钨环丁二烯缺乏反应性。钳N原子的孤对电子与W之间的重要粘结组合
• [EN] TRIDENTATE PINCER LIGAND SUPPORTED METAL-ALKYLIDYNE AND METALLACYCLOALKYLENE COMPLEXES FOR ALKYNE POLYMERIZATION<br/>[FR] COMPLEXES MÉTAL-ALKYLIDYNE ET MÉTALLACYCLOALKYLÈNE SUPPORTÉS SUR DES LIGANDS PINCES TRICOORDINÉS POUR LA POLYMÉRISATION D'ALCYNES
  申请人：UNIV FLORIDA

  公开号：WO2013085707A1

  公开（公告）日：2013-06-13

  Tridentate pincer ligand supported metal complexes are formed where the complex is a trianionic pincer ligand supported metal-alkylidyne complex or a tetraanionic pincer-ligand supported metallacycloalkylene complex formed by addition of an alkyne to the trianionic pincer ligand supported metal-alkylidyne complex. The tridentate pincer ligand supported metal complex that includes a group 5-7 transition metal and an OCO trianionic pincer ligand or an alkyne adduct thereof and methods of preparing the complexes are disclosed. The use of the tridentate pincer ligand supported metal complex for the polymerization of alkynes is disclosed, where high molecular weight poly(alkyne)s can be formed in high yield.

  三齿夹持配体支持的金属配合物形成，其中该配合物是一个三阴离子夹持配体支持的金属-烷基炔基配合物或通过将炔烃加到三阴离子夹持配体支持的金属-烷基炔基配合物形成的四阴离子夹持金属环烯烃配合物。揭示了包括5-7族过渡金属和OCO三阴离子夹持配体或其炔基加合物的三齿夹持配体支持的金属配合物以及配合物的制备方法。还揭示了三齿夹持配体支持的金属配合物用于炔烃的聚合，可以高产率地形成高分子量的聚烯烃。
• Is it possible to stabilise complexes with a tungsten–phosphorus triple bond?
  作者：Manfred Scheer、Kay Schuster、Theodore A. Budzichowski、Malcolm H. Chisholm、William E. Streib

  DOI：10.1039/c39950001671

  日期：——

  [W(CO)2η4-(But2C2P2)W(CO)5}η-2-(ButCP)W(CO)5}]1 is prepared by treatment of ButCP with [W(CO)5THF]; the reaction of [W2(OBut)6] with ButCP in the presence of [M(CO)5THF](M = Cr, W) affords novel compounds of the type [(ButO)3WP→M(CO)5](M = Cr, W), the first examples of a formal WP containing complex.

  [W(CO)2η4-(But2C2P2)W(CO)5}η-2-(ButCP)W(CO)5}]1 通过用 [W(CO)5THF 处理 ButCP 来制备]; [W2(OBut)6] 与 ButCP 在 [M(CO)5THF](M = Cr, W) 存在下反应，得到 [(ButO)3WP→M(CO)5]( M = Cr, W)，第一个包含配合物的正式 WP 示例。