bis(1,2,3,4-tetramethylcyclopentadienyl)zirconium dichloride | 119445-90-8

• 物质功能分类: 化学试剂 - 有机试剂 - 烯烃（环状与无环状）
• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: bis(1,2,3,4-tetramethylcyclopentadienyl)zirconium dichloride
• 英文别名: (η(5)-tetramethylcyclopentadienyl)ZrCl2；(η(5)-C5HMe4)2ZrCl2；(η5-C5Me4H)2ZrCl2；(η⁵-C₅Me₄H)₂ZrCl₂；(η5-C5Me4H)2 zirconium(IV) dichloride；(Cp-Me4)2ZrCl2；1,2,3,5-Tetramethylcyclopenta-1,3-diene;zirconium(4+);dichloride；1,2,3,5-tetramethylcyclopenta-1,3-diene;zirconium(4+);dichloride
• CAS: 119445-90-8
• 化学式: C₁₈H₂₆Cl₂Zr
• 分子量: 404.534
• InChiKey: MAALGNWGAOOGNY-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.65
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 安全说明：
  S24/25
• 储存条件：
  2-8°C，充入氩气。

SDS

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Section 1: Product Identification
Chemical Name: Bis(tetramethylcyclopentadienyl)zirconium dichloride, min. 97%
CAS Registry Number: 119445-90-8
Formula: [(CH3)4C5H]2ZrCl2
EINECS Number: none
Chemical Family: metallocene
Synonym: Zirconium, bis[1,2,3,4,5-.ete.)-1,2,3,4-tetramethyl-2,4-cyclopentadiene-1-yl]dichloro

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 119445-90-8 100% 5mg/m3 (as Zr) 5mg/m3 (as Zr)

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin and eyes. May be irritating to respiratory tract.
Primary Routes of Exposure: skin, eyes, ingestion
Eye Contact: Causes moderate irritation of the eyes.
Skin Contact: Causes moderate irritation of the eyes.
Inhalation: May be irritating to the nose, mucous membranes and respiratory tract.
Ingestion: No information on the physiological effects of ingestion.
Exposure to moisture slowly produces hydrochloric acid. Irritating to skin, eyes. May be irritating to the
Acute Health Affects:
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 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 in
Inhalation:
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: none
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: carbon dioxide, foam or dry powder
If this product is involved in a fire, firefighters should be equipped with NIOSH approved positive pressure
Special Fire Fighting Procedures:
self-contained breathing apparatus.
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
Small spills can be mixed with calcium carbonate, sodium bicarbonate or other appropriate acid neutralizing
Spill and Leak Procedures:
non combustible solid and swept up.

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SECTION 7: Handling and Storage
The material will degrade on prolonged exposure to moisture. Keep bottle tightly sealed and away from heat
Handling and Storage:
and light. Handle in a dry atmosphere.

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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: 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 powder
Molecular Weight: 404.53
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: may have an acidic odor
Solubility in Water: reacts with water

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SECTION 10: Stability and Reactivity
Stability: moisture-sensitive solid
Hazardous Polymerization: No hazardous polymerization.
Conditions to Avoid: exposure to moisture
Incompatibility: water, strong oxidizing agents
Decomposition Products: carbon dioxide, carbon monoxide, hydrogen chloride, organic fumes and zirconium oxide

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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：

  bis(1,2,3,4-tetramethylcyclopentadienyl)zirconium dichloride 在 一氧化碳 、 magnesium 、 mercury dichloride 作用下， 以 四氢呋喃 为溶剂， 以65%的产率得到(η5-C5Me4H)2Zr(CO)2
  参考文献：
  名称：

  制备配合物[（C 5 Me 4 H）2 MX 2 ]（M + Ti，Zr； X + Cl，烷基，芳基，CO）。练习曲RMN dynamique de lagênestériqueàla rotation des groupements aryleliésaumétal

  摘要：

  新的配体C 5 Me 4 H与[TiCl 3 ]或[ZrCl 4 ]反应，得到二氯配合物[（C 5 Me 4 H）2 MCl 2 ]（MTi，Zr）和三氯配合物[（C 5 Me 4 H）-TiCl 3 ]。这些配合物的RLi，或CO下其减少的治疗，给人的衍生物[（C 5我4 1H）1）MR 2 ]（RCH 3，C 6 H ^ 5，p -C 6 H ^ 4 CH3，CO）。还描述了新系列化合物[（C 5 Me 4 H）（C 5 H 5）TiR 2 ]的制备。的C的电子效应5我4 ħ配体类似密切与C 5我5。1 H和13 C NMR芳族信号的合并表明，芳基核围绕金属-碳键的旋转由于芳基络合物中C 5 Me 4 H配体的大尺寸而受到限制。已为[（C 5 Me4 H）2 Ti（p -C 6 H 4 CH 3）2 ]。

  DOI：

  10.1016/0022-328x(89)85262-3
• 作为产物：
  描述：

  氯化锆(IV) 在 C₅H₂Me₄ 、 BuLi 、 HCl 作用下， 以 正己烷 、 水 、 甲苯 为溶剂， 以55%的产率得到bis(1,2,3,4-tetramethylcyclopentadienyl)zirconium dichloride
  参考文献：
  名称：

  Methyl-Substituted Zirconocene−Bis(trimethylsilyl)acetylene Complexes (C₅H_5-nMe_n)₂Zr(η²-Me₃SiC⋮CSiMe₃) (n = 2−5)

  摘要：

  The (C(5)H(5-n)Me(n))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (n = 2-5; 1,3-dimethyl, 1,2,3-trimethyl) (2C-F) complexes were prepared by the reduction of corresponding zirconocene dichlorides with magnesium in THF in the presence of bis(trimethylsilyl)acetylene (BTMSA). All of them are stable in the absence of THF. Crystal structures of (C(5)HMe(4))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (2E) and (C(5)Me(5))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (2F) and ofthe analogous titanium complexes are isomorphous. The red shift of the nu(C=C) vibration and the downfield shift of C-13 delta(C=C) indicate that BTMSA in 2C-F is more strongly coordinated than in analogous titanocene complexes. The nonisolated complex (C(5)H(4)Me)(2)Zr[eta(2)-C-2(SiMe(3))(2)](THF) (2B . THF) rearranges after the loss of THF to give the dimer [(eta(5)-C(5)H(4)Me)(eta(1)-C(SiMe(3))=CH(SiMe(3))Zr(mu-eta(1):eta(5)-C(5)H(3)Me)](2) (3B).

  DOI：

  10.1021/om960184j

文献信息

• Dinitrogen Functionalization with Terminal Alkynes, Amines, and Hydrazines Promoted by [(η⁵-C₅Me₄H)₂Zr]₂(μ₂,η²,η²-N₂):  Observation of Side-On and End-On Diazenido Complexes in the Reduction of N₂ to Hydrazine
  作者：Wesley H. Bernskoetter、Jaime A. Pool、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/ja050387b

  日期：2005.6.1

  Functionalization of the N2 ligand in the side-on bound dinitrogen complex, [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2), has been accomplished by addition of terminal alkynes to furnish acetylide zirconocene diazenido complexes, [(eta5-C5Me4H)2Zr(C[triple bond]CR)]2(mu2,eta2,eta2-N2H2) (R = nBu, tBu, Ph). Characterization of [(eta5-C5Me4H)2Zr(C[triple bond]CCMe3)]2(mu2,eta2,eta2-N2H2) by X-ray diffraction

  N2 配体在侧向结合的二氮复合物 [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2) 中的功能化已经通过添加末端炔来提供乙炔锆茂二氮杂复合物 [( eta5-C5Me4H)2Zr(C[三键]CR)]2(mu2,eta2,eta2-N2H2) (R = nBu, tBu, Ph)。[(eta5-C5Me4H)2Zr(C[三键]CCMe3)]2(mu2,eta2,eta2-N2H2) 的 X 射线衍射表征揭示了固态的侧面结合的二氮杂配体，而可变温度1H 和 15N NMR 研究确定了溶液中 [N2H2]2-配体的 eta1,eta1 和 eta2,eta2 触觉之间的快速互变。合成烷基、卤化物和三氟甲碳茂二氮杂化合物 [(eta5-C5Me4H)2ZrX]2(mu2,eta1,eta1-N2H2) (X = Cl, I, OTf, CH2Ph, CH2SiMe3), 得到
• Synthesis, structural characterization and reactivity of new tin bridged ansa-bis(cyclopentadiene) compounds: X-ray crystal structures of Me2Sn(C5Me4R-1)2 (R=H, SiMe3)
  作者：Santiago Gómez-Ruiz、Sanjiv Prashar、Mariano Fajardo、Antonio Antiñolo、Antonio Otero

  DOI：10.1016/j.jorganchem.2007.03.031

  日期：2007.6

  The organo-tin compounds, Me2Sn(C5H4R-1)2 (R = Me (1), Pri (2), But (3), SiMe3 (4)) and Me2Sn(C5Me4R-1)2 (R = H (5), SiMe3 (6)), were prepared by the reaction of Me2SnCl2 with the lithium or sodium derivative of the corresponding cyclopentadiene. Compounds 1–6 have been characterized by multinuclear NMR spectroscopy (1H, 13C, 119Sn). In addition the molecular structures of 5 and 6 were determined by

  的有机锡化合物中，Me 2的Sn（C 5 H ^ 4 R-1）2（R =我（1），PR我（2），卜吨（3），森达3（4））和Me 2 SN（通过使Me 2 SnCl 2与相应的环戊二烯的锂或钠衍生物反应来制备C 5 Me 4 R-1）2（R = H（5），SiMe 3（6））。化合物1 - 6已经通过多核NMR光谱法（1 H，13 C，119 Sn）表征。另外，通过单晶X射线衍射研究确定了5和6的分子结构。的转移金属化反应1 - 6用的ZrCl 4或[NbCl 4（THF）2 ]，得到相应的金属茂配合物以高产率。
• Photochemically Induced Reductive Elimination as a Route to a Zirconocene Complex with a Strongly Activated N₂Ligand
  作者：Grant W. Margulieux、Scott P. Semproni、Paul J. Chirik

  DOI：10.1002/anie.201402401

  日期：2014.8.25

  The zirconocene dinitrogen complex [(η5‐C5Me4H)2Zr}2(μ2,η2,η2‐N2)] was synthesized by photochemical reductive elimination from the corresponding zirconium bis(aryl) or aryl hydride complexes, providing a high‐yielding, alkali metal‐free route to strongly activated early‐metal N2 complexes. Mechanistic studies support the intermediacy of zirconocene arene complexes that in the absence of sufficient

  茂锆二氮络合物[（η 5 -C 5我4 1H）2的Zr} 2（μ 2，η 2，η 2 -N 2）]通过光化学还原消除从相应的锆，双（芳基）或芳基合成氢化物配合物，为强活化的早期金属N 2配合物提供了一种高产，无碱金属的途径。机理研究支持中间性的锆芳烃络合物，在没有足够的二氮促进Ç  ħ激活或经历comproportion正式的Zr III络合物。当N 2 过量的芳烃置换会引起强烈的二氮活化。
• Preparation and Characterization of Monomeric and Dimeric Group IV Metallocene Dihydrides Having Alkyl-Substituted Cyclopentadienyl Ligands
  作者：Paul J. Chirik、Michael W. Day、John E. Bercaw

  DOI：10.1021/om9810293

  日期：1999.5.1

  3-(CHMe2)2}ZrH2 and (η5-C5HMe4)2ZrH2 exist as equilibrium mixtures of monomer and dimer in benzene solution. The hydride ligands rapidly exchange with D2, affording the dideuteride complexes. Deuterium incorporation into some of the substituents on the cyclopentadienyl rings of the monomeric dihydride complexes is also observed. The X-ray structures of Cp*2HfH2, Cp*η5-C5H4(CMe3)}ZrCl2, Cp*η5-C5H3-1,3-(CHMe2)2}ZrCl2

  通过氢化相应的二甲基配合物，制备了一系列具有[R n CP）2 ZrH 2 ] x的具有取代的环戊二烯基配体的一系列锆茂二氢化物配合物。最拥挤空间成员（CP *（η 5 -C 5 HME 4）ZRH 2，（CP * =（η 5 -C 5我5））中，CP * η 5 -C 5 H ^ 3 -1,3- （CME 3）2 } ZRH 2和η 5 -C 5 H ^ 3 -1,3-（CME3）2 } 2 ZrH 2）是单体；那些不太拥挤的构件（的[CP * η 5 -C 5 H ^ 4（CME 3）} ZRH 2 ] 2，混合[CP *（THI）ZRH 2 ] 2（THI =η 5 -tetrahydroindenyl），和[η 5 -C 5 H 3 -1,3-（CHME 2）2 } 2 ZrH 2 ] 2）在苯溶液中主要为二聚体。的CP * η 5 -C 5 H ^ 3 -1,3-（CHME2）2
• Addition of Methyl Triflate to a Hafnocene Dinitrogen Complex: Stepwise N₂ Methylation and Conversion to a Hafnocene Hydrazonato Compound
  作者：Donald J. Knobloch、David Benito-Garagorri、Wesley H. Bernskoetter、Ivan Keresztes、Emil Lobkovsky、Hannah Toomey、Paul J. Chirik

  DOI：10.1021/ja904436a

  日期：2009.10.21

  addition yields a variety of products that lack new nitrogen-carbon bonds. The methylated hafnocene product, (eta(5)-C(5)Me(4)H)(2)Hf(OTf)(N(2)(CH(3))) provides a platform for additional transformations for the functionalized dinitrogen core. Treatment with additional methyl triflate results in a second nitrogen-carbon bond formation to yield a rare example of a triflato hafnocene hydrazonato complex. Loss

  处理带有强烈活化的侧向结合二氮配体 [(eta(5)-C(5)Me(4)H)(2)Hf](2)(mu(2),eta( 2),eta(2)-N(2))，用两当量的三氟甲磺酸甲酯生成混合物，其中一种被鉴定为三氟甲磺酸铪甲基二氮杂化合物，(eta(5)-C(5)Me (4)H)(2)Hf(OTf)(N(2)(CH(3)))，由其中一个氮原子的甲基化产生。这种反应性与二茂锆同系物 [(eta(5)-C(5)Me(4)H)(2)Zr](2)(mu(2),eta(2),eta(2) -N(2))，其中添加三氟甲磺酸甲酯会产生多种缺乏新氮碳键的产物。甲基化铪产物 (eta(5)-C(5)Me(4)H)(2)Hf(OTf)(N(2)(CH(3))) 为功能化二氮的额外转化提供了平台核。用额外的三氟甲磺酸甲酯处理导致形成第二个氮碳键，从而产生三氟甲磺酸铪腙腙络合物的罕见例子。甲烷的损失和铪二三氟甲磺酸盐的形