双茚基锆(VI)二氯化合物 | 12148-49-1

• 分子结构分类: 有机化合物 - 苯类化合物
• 中文名称: 双茚基锆(VI)二氯化合物
• 中文别名: 二茚基二氯化锆；二氯双茚基锆(VI)
• 英文名称: bis(indenyl)zirconium(IV) dichloride
• 英文别名: bis(indenyl)zirconium dichloride；Ind₂ZrCl₂；Dichlorozirconium(2+);inden-7a-ide；dichlorozirconium(2+);inden-7a-ide
• CAS: 12148-49-1
• 化学式: C₁₈H₁₄Cl₂Zr
• 分子量: 392.439
• InChiKey: OLWNTZDHHWRPPI-UHFFFAOYSA-L

物化性质

• 熔点：
  239-243 °C(lit.)

计算性质

• 辛醇/水分配系数(LogP)：
  6.49
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  4.0
• 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：
  2

安全信息

• 危险品标志：
  C
• 安全说明：
  S26,S27,S36/37/39,S45
• 危险类别码：
  R15
• 海关编码：
  2903999090
• 危险品运输编号：
  UN 3261 8/PG 3
• 储存条件：
  存储条件为：2-8°C，避光，惰性气体保护。

SDS

Name:	Dichlorobis(indenyl)zirconium(IV) Material Safety Data Sheet
Synonym:
CAS:	12148-49-1

Section 1 - Chemical Product MSDS Name:Dichlorobis(indenyl)zirconium(IV) Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
12148-49-1	Dichlorobis(indenyl)zirconium(IV)		unlisted

Hazard Symbols: C
Risk Phrases: 15 34

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Contact with water liberates extremely flammable gases. Causes burns.Moisture sensitive.Air sensitive.
Potential Health Effects
Eye:
Causes eye burns.
Skin:
Causes skin burns.
Ingestion:
Causes gastrointestinal tract burns.
Inhalation:
Causes chemical burns to the respiratory tract.
Chronic:
Not available.

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Section 4 - FIRST AID MEASURES
Eyes: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid immediately.
Skin:
Get medical aid immediately. Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes.
Ingestion:
Get medical aid immediately. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water.
Inhalation:
Get medical aid immediately. Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen.
Notes to Physician:
Treat symptomatically and supportively.

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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. Water hydrolyzes material liberating acidic gas which in contact with metal surfaces can generate flammable and/or explosive hydrogen gas.
Extinguishing Media:
DO NOT USE WATER! In case of fire, use carbon dioxide, dry chemical powder or appropriate foam.

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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. Avoid generating dusty conditions. Isolate area and deny entry.

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Section 7 - HANDLING and STORAGE
Handling:
Do not breathe dust, vapor, mist, or gas. Do not get in eyes, on skin, or on clothing. Use and store under nitrogen. Use only in a chemical fume hood.
Storage:
Store in a cool, dry place. Store in a tightly closed container.
Keep away from water. Corrosives area. Store under nitrogen.

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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# 12148-49-1: 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.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Solid
Color: Not available.
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 239-243 deg C
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: C18H14Cl2Zr
Molecular Weight: 392.43

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not available.
Conditions to Avoid:
Incompatible materials, exposure to air, exposure to moist air or water.
Incompatibilities with Other Materials:
Strong oxidizing agents, acids, bases, chemically active metals.
Hazardous Decomposition Products:
Hydrogen chloride, carbon monoxide, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 12148-49-1 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Dichlorobis(indenyl)zirconium(IV) - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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

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Section 14 - TRANSPORT INFORMATION

IATA
Shipping Name: Corrosive solid, acidic, organic, n.o.s.*
Hazard Class: 8
UN Number: 3261
Packing Group: III
IMO
Shipping Name: Corrosive solid, acidic, organic, n.o.s.
Hazard Class: 8
UN Number: 3261
Packing Group: III
RID/ADR
No information available.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: C
Risk Phrases:
R 15 Contact with water liberates extremely
flammable gases.
R 34 Causes burns.
Safety Phrases:
S 7/8 Keep container tightly closed and dry.
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# 12148-49-1: No information available.
Canada
CAS# 12148-49-1 is listed on Canada's NDSL List.
CAS# 12148-49-1 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 12148-49-1 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  双茚基锆(VI)二氯化合物 在 (CH₃CO)2CH₂ 作用下， 以 neat (no solvent) 为溶剂， 以29%的产率得到
  参考文献：
  名称：

  Exchange reactions in series of zirconium and hafnium organometallic compounds, containing chelate ligands

  摘要：

  DOI：

  10.1007/bf00949603
• 作为产物：
  描述：

  bis(indenyl)zirconium dimethyl 、 二氯化硫 以 甲苯 为溶剂， 以91.4%的产率得到双茚基锆(VI)二氯化合物
  参考文献：
  名称：

  双（茚基）二卤化锆的反直觉而有效的合成

  摘要：

  描述了双茚基锆二甲基锆在相应的二卤化物的合成中的用途。Ind 2 ZrCl 2的合成已经通过各种无机氯化物（包括BCl 3，甲苯或二氯甲烷中的SCl 2和在Et中的HCl ）氯化Ind 2 ZrMe 2（2）的方法，干净，定量地进行了合成。2 O.后一种方法是优选的一个，因为它产生甲烷作为唯一的副产品，并且所形成的工业2的ZrCl 2与ET沉淀定量2O溶剂：简单过滤即可定量获得分析纯的产物。Ind 2 ZrBr 2和Ind 2 ZrI 2分别通过2与Br 2和I 2反应获得。与经典方法相比，通过氯化二甲基茂金属“衍生物”的“逆”合成法具有以下优势：第一，Ind 2 ZrCl 2以较高的收率（90-96％）获得；第二，它更易于纯化（在二甲基阶段），并且不含LiCl。在溶液丙烯聚合中，已经研究了五个具有不同sigma配体的双茚基锆配合物：发现σ-配体对催化剂活性或聚合物性能均无相关影响。

  DOI：

  10.1016/s0022-328x(03)00124-4
• 作为试剂：
  描述：

  2,3-苯并呋喃 、 (HC[(CMe)N(2,4,6-Me3C6H2)]2)AlH2 在 二苯并呋喃 、 双茚基锆(VI)二氯化合物 、 3,3-二甲基-1-丁烯 作用下， 以 氘代苯 为溶剂， 反应 48.0h， 以67%的产率得到
  参考文献：
  名称：

  A Highly Chemoselective, Zr-Catalyzed C–O Bond Functionalization of Benzofuran

  摘要：

  The chemoselective C-O bond functionalization of benzofuran with an aluminum dihydride may be catalyzed by zirconocene dichlorides. The reaction proceeds with the formal addition of a C-O bond to, and elimination of dihydrogen from, aluminum. The product of C-O bond alumination reacts with benzaldehyde via insertion of the carbonyl into the newly formed Al-C bond.

  DOI：

  10.1021/om4008295

文献信息

• Zirconocene dichlorides as catalysts in alkene carbo- and cyclometalation by AlEt₃: intermediate structures and dynamics
  作者：Lyudmila V. Parfenova、Pavel V. Kovyazin、Olesia V. Mukhamadeeva、Pavel V. Ivchenko、Ilya E. Nifant'ev、Leonard M. Khalilov、Usein M. Dzhemilev

  DOI：10.1039/d1dt03160k

  日期：——

  A series of zirconocenes L2ZrCl2 (23 examples) were studied as catalysts in the reaction of alkenes with AlEt3. The catalyst activity and reaction chemoselectivity were found to depend on the ligand structure in the complex and the nature of the solvent. The alkyl exchange in the triethylaluminum dimer was studied by NMR spectroscopy; a solvent effect on the alkyl exchange parameters was established

  研究了一系列二茂锆 L 2 ZrCl 2（23 个实施例）作为烯烃与 AlEt 3反应的催化剂。发现催化剂活性和反应化学选择性取决于配合物中的配体结构和溶剂的性质。三乙基铝二聚体中的烷基交换通过核磁共振光谱研究；确定了溶剂对烷基交换参数的影响。L 2 ZrCl 2与AlEt 3反应生成中间体L 2 ZrEtCl、L 2 Zr(μ-Cl)CH 2 CH 2 AlEt 2、L 2 Zr(μ-H)CH显示了2 CH 2 AlEt 2和L 2 Zr(μ-Cl)CH 2 CH(AlEt 2 ) 2；中间体的比例取决于初始配合物中的配体结构和溶剂。在乙二基桥ZrCH交换2 CH 2的Al，则进行经由zirconocenecyclopropane结构，被证明为在第一时间为五元双金属络合物大号2的Zr（μ-Cl）的CH 2 CH 2 ALET 2与柄-ligands（L 2 = Me 2 SiCp 2 ,
• Selective Halodemethylation Reactions of Metallocene Dimethyls with Triphenylmethyl Chloride and Benzyl Bromide
  作者：Eric J. Hawrelak、Paul A. Deck

  DOI：10.1021/om0305014

  日期：2004.1.1

  NMR-scale reactions of several group 4 metallocene dimethyls with either trityl chloride or benzyl bromide gave the corresponding L2M(Me)X complexes selectively. Five reactions, including syntheses of Cp2Zr(Me)Cl and Ind2Zr(Me)Cl, were conducted on a preparative scale to afford useful isolated yields of L2M(Me)Cl complexes.

  几种4号茂金属二甲基与三苯甲基氯或苄基溴的NMR规模反应选择性地产生了相应的L 2 M（Me）X络合物。在制备规模上进行了五个反应，包括Cp 2 Zr（Me）Cl和Ind 2 Zr（Me）Cl的合成，以提供有用的L 2 M（Me）Cl复合物的分离产率。
• Novel Synthesis of Zirconocene Difluoride and Alkyl Monofluoride Complexes
  作者：Anke Spannenberg、Perdita Arndt、Wolfgang Baumann、Vladimir V. Burlakov、Uwe Rosenthal、Sigurd Becke、Thomas Weiss

  DOI：10.1021/om049745u

  日期：2004.8.1

  methods for preparation of the zirconocene difluorides rac-(ebthi)ZrF2 (7), (thi)2ZrF2 (8), Me4C2(η5-C5H4)2ZrF2 (9), and Me2Si(η5-C9H10)2ZrF2 (10) and the monofluorides Cp2Zr(F)(CH2CH2-2-Py) (11), rac-(ebthi)Zr(F)(CH2CH2-2-py) (12), (thi)2Zr(F)(CH2CH2-2-py) (13), Me2Si(η5-C5H4)2Zr(F)(CH2CH2-2-py) (14), and Me2Si(η5-C9H10)2ZrF(Me) (15) are reported and compared. The molecular structures of the bis-

  从茂锆双开始（三甲基甲硅烷基）乙炔络合物CP“ 2的Zr（L）（η 2经由-btmsa）的2-乙烯基吡啶络合物CP” 2的Zr（2- vipy）用于二茂锆和二氟一氟化烷基络合物得到阐述一个新的合成方法。与选定的配体不同系统的Cp”实施例2混合[Cp 2 =双（η 5 -环戊二烯基）; ebthi = 1,2-亚乙基- 1,1'-双（η 5 -tetrahydroindenyl）; （THI）2 =双（η 5 -tetrahydroindenyl）; 我2的Si（η 5 -C 5 H ^ 4）2 =二甲基甲硅烷（η 5-环戊二烯基）；（ⅰ）2 =双（η 5 -茚基）; EBI = 1,2-亚乙基- 1,1'-双（η 5 -茚基）; 和Me 2的Si（η 5 -C 9 ħ 10）2 =二甲基甲硅烷基-1,1'-双（η 5 -tetrahydroindenyl）]合成的。在一系列这些调查的新配合物（I）2的Zr（THF）（η
• Reactive Intermediates of the Catalytic Carbomagnesation Reaction:  Isolation and Structures of [Cp₂ZrEt]₂(μ-ethene), [Cp₂Zr(ethene)(L)] (L = THF, Pyridine), and [(indenyl)₂Zr(ethene)(THF)] and of Metallacycles with Norbornene
  作者：Reinald Fischer、Dirk Walther、Peter Gebhardt、Helmar Görls

  DOI：10.1021/om0001669

  日期：2000.6.1

  complexes [(indenyl)2Zr(ethene)(THF)] (4) and [Cp2Zr(ethene)(pyridine)] (5) were analogously prepared in good yield. The X-ray structure of the dark red complex 4 shows that the zirconium atom, the two carbons of ethene, and the oxygen donor atom of THF lie in a single plane. The C−C bond distance of the coordinated ethene is elongated to 1.451(5) Å. Complex 3 undergoes a fast reaction with norbornene to

  Cp 2 ZrCl 2和EtMgCl 2当量在THF中在0°C之间的反应导致双核络合物[Cp 2 Zr（Et）] 2（μ-乙烯）（1）的形成，收率很高。X射线晶体结构确定为1表示桥接的乙烯可以视为二价阴离子C 2 H 4 2 ，它与两个相邻的Cp 2 Zr（Et）中心不对称配位。类似的配合物[（ME 3的Si-CP）2锆（ET）] 2（μ-乙烯）（2）从反应中分离（ME 3Si-Cp）2 ZrCl 2和2当量的EtMgCl。通过在0℃以下在THF中使Cp 2 ZrCl 2和Et 2 Mg（二恶烷）反应，得到单核橙色化合物[Cp 2 Zr（乙烯）（THF）]（3）。在0°C下THF- d 8中3的1 H NMR光谱中，仅观察到两个单峰（分别为5.46和0.51 ppm），分别对应于Cp和乙烯质子。此外，通过在-90℃下的X射线晶体学测定其固态的结构基序。密切相关的配合物[（茚基）2 Zr（乙烯）（THF）]（4）和[Cp
• An NMR study on the reaction of substituted dimethyl zirconocenes with dimethylanilinium borate
  作者：Luca Rocchigiani、Gianfranco Bellachioma、Cristiano Zuccaccia、Alceo Macchioni

  DOI：10.1016/j.jorganchem.2012.02.011

  日期：2012.9

  The reaction of a series of dimethyl zirconocenes [Me2Si(Cp)2ZrMe2, 1; Cpt−bu2ZrMe2, 2; Cpn−bu2ZrMe2, 3; Ind2ZrMe2, 4; CpMe42ZrMe2, 5; Cp∗2ZrMe2, 6] with [HNMe2Ph][B(C6F5)4] was investigated by means of NMR spectroscopy. It was found that protonolysis of a Zr–Me group occurred generating a coordinative vacancy at the metal center and methane. Cations coming from 1–4 dimethyl precursors bound NMe2Ph

  一系列二甲基二茂锆的反应〔我2的Si（CP）2 ZrMe 2，1 ; CP叔BU 2 ZrMe 2，2 ; CP正丁基2 ZrMe 2，3 ; IND 2 ZrMe 2，4 ; 的Cp ME4 2 ZrMe 2，5 ; 的Cp * 2 ZrMe 2，6 ]与[HNME 2 PH] [B（C 6 ˚F 5）4通过NMR光谱法研究了[α]。发现Zr-Me基团的质子分解在金属中心和甲烷处产生协调的空位。阳离子从未来1 - 4个结合的NME二甲前体2的pH值，从质子化过程中释放，并形成zirconaaziridinium离子对[我2的Si（CP）2锆（η 2 -CH 2 NMePh）] [B（C 6 ˚F 5）4 ]，7 ; 的[Cp叔BU 2的Zr（η 2 -CH 2 NMePh）] [B（C 6 ˚F 5）4 ]，8；的[Cp正丁基2的Zr（η 2 -CH 2 NMePh）] [B（C 6 ˚F