溴化锆(IV) | 13777-25-8

• 物质功能分类: 无机化工 - 无机盐 - 金属卤化物及卤酸盐
• 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: 溴化锆(IV)
• 中文别名: 溴化锆
• 英文名称: zirconium(IV) bromide
• 英文别名: ZrBr₄；zirconium tetrabromide；zirconium bromide；Zirconium(4+);tetrabromide
• CAS: 13777-25-8
• 化学式: Br₄Zr
• 分子量: 410.84
• InChiKey: LSWWNKUULMMMIL-UHFFFAOYSA-J

物化性质

• 熔点：
  450°C
• 沸点：
  360°C (estimate)
• 密度：
  4,201 g/cm3
• 溶解度：
  与H2O反应
• 暴露限值：
  ACGIH: TWA 5 mg/m3; STEL 10 mg/m3NIOSH: IDLH 25 mg/m3; TWA 5 mg/m3; STEL 10 mg/m3
• 稳定性/保质期：

  在常温常压下保持稳定，应避免与以下物质接触：水分或潮湿环境、酸类（尤其是具有吸湿性的酸），这些物质可能导致其分解。

计算性质

• 辛醇/水分配系数(LogP)：
  3.38
• 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

ADMET

毒理性

• 副作用

Dermatotoxin - 皮肤烧伤。

Dermatotoxin - Skin burns.

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

安全信息

• TSCA：
  Yes
• 危险等级：
  8
• 危险品标志：
  C
• 安全说明：
  S22,S26,S27,S36/37/39,S45
• 危险类别码：
  R20/21/22
• WGK Germany：
  3
• 危险品运输编号：
  UN 3260 8/PG 2
• 包装等级：
  III
• 危险类别：
  8
• 危险标志：
  GHS05
• 危险性描述：
  H314
• 危险性防范说明：
  P280,P305 + P351 + P338,P310
• 储存条件：
  常温密闭保存，置于阴凉、通风干燥的惰性气体环境中。

SDS

---

Section 1: Product Identification
Chemical Name: Zirconium (IV) bromide, 98% (99+%-Zr)
CAS Registry Number: 13777-25-8
Formula: ZrBr4
EINECS Number: 237-417-4
Chemical Family: metal halide
Synonym: Zirconium tetrabromide

---

Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title Compound 13777-25-8 100% 5mg/m3 (as Zr) 5mg/m3 (as Zr)

---

Section 3: Hazards Identification
With moisture, this material becomes a strong, corrosive acid. The liquid and its vapor are extremely corrosive
Emergency Overview:
to skin, eyes, mucous membranes and respiratory tract.
Primary Routes of Exposure: Ingestion, inhalation, eyes and skin
Eye Contact: Severe corrosive to the eyes. Exposure can lead to permanent eye damage.
Skin Contact: Corrosive to skin. Contact can lead to redness, pain, blistering, ulceration, and scar formation.
Material releases corrosive fumes. Severe burning of the mucous membranes and lungs. Pulmonary edema
Inhalation:
may occur.
Product is a highly corrosive acid. Ingestion may cause pain, vomiting, burns of mouth and throat, and
Ingestion:
ulceration of gastrointestinal tract.
Acute Health Affects: Severe corrosive to eyes, skin, mucous membranes and respiratory tract. Ingestion may be fatal.
Repeated or prolonged exposure to bromides by any route may cause skin rashes (bromaderma) and central
Chronic Health Affects:
nervous system depression, including ataxia, psychoses, memory loss, irritability, and headache.
NTP: No
IARC: No
OSHA: No

---

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.

---

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 none
Decomposion Products:
Unusual Fire or Explosion Hazards: No unusual fire or explosion hazards.

---

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.

---

SECTION 7: Handling and Storage
Store solid in a tightly sealed container away from moisture. Handle in a fume hood under a dry atmosphere of
Handling and Storage:
air or nitrogen. Prolonged exposure to the atmosphere may degrade the product.

---

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.

---

SECTION 9: Physical and Chemical Properties
Color and Form: off-white pwdr.
Molecular Weight: 410.86
Melting Point: 450° (15 atm)
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: 4.201
Odor: pungent odor
Solubility in Water: reacts with water

---

SECTION 10: Stability and Reactivity
Stability: moisture sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: contact with moisture
Incompatibility: water, mineral acids and active metals
Decomposition Products: none

---

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

---

SECTION 12: Ecological Information
Ecological Information: No information available

---

SECTION 13: Disposal Considerations
Disposal: Dispose of according to local, state and federal regulations.

---

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

---

SECTION 15: Regulatory Information
TSCA: Listed in the TSCA inventory.
SARA (Title 313): Title compound not listed.
Second Ingredient: none

---

SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

制备方法

将锆粉末加热至850℃，以稀有气体为载气通入溴气，即可制得四溴化锆。或者将ZrO₂与碳按1∶2的比例混合，加热该混合物至650℃，同样以稀有气体为载气通入溴气，也能得到四溴化锆。此过程中的反应装置和操作方法与合成四氯化锆相同。

合成制备方法

将锆粉末加热至850℃，以稀有气体为载气通入溴气，即可制得四溴化锆。或者将ZrO₂与碳按1∶2的比例混合，加热该混合物至650℃，同样以稀有气体为载气通入溴气，也能得到四溴化锆。此过程中的反应装置和操作方法与合成四氯化锆相同。

用途简介

（此处内容为空）

反应信息

• 作为反应物：
  描述：

  溴化锆(IV) 以 neat (no solvent) 为溶剂， 生成 锆
  参考文献：
  名称：

  Boer, J. H. de; Fast, J. D., Zeitschrift fur anorganische Chemie, 1926, vol. 153, p. 1 - 8

  摘要：

  DOI：
• 作为产物：
  描述：

  氯化锆(IV) 在 氢溴酸 作用下， 以 乙醚 、 正庚烷 为溶剂， 以32%的产率得到溴化锆(IV)
  参考文献：
  名称：

  锆（II）和ha（II）的芳烃衍生物

  摘要：

  无水四卤化物MX 4（M = Zr或Hf，X = Br或I）的制备方法是，将M（BH 4）4用干燥的HX在正庚烷中作为溶剂处理，然后在减压下升华。ZrCl 4与Al–AlCl 3 –芳烃体系的反应导致溶液中含有锆（II）–芳烃配合物。对于苯和六甲基苯（在苯中），获得了组成为Zr（亚芳基）（AlCl 4）2的固体物质。根据光谱性质，化学反应性和其他数据，这些物质被认为是锆（II）衍生物，其结构与相应的钛（II）配合物已经建立的结构相似。锆（II）的六甲基苯配合物也可以通过[Zr（C 6 H 6）（AlCl 4）2 ]和丁-2-炔的配位体合成反应获得。获得了相应of（II）–η 6-芳烃配合物（芳烃=甲苯或均三甲苯）在溶液中存在的光谱证据。三核物种中，[Zr 3氯6（η 6 -C 6我6）3 ] Ñ +（n = 1或2）是通过Al-AlCl 3还原ZrCl 4（n = 2）或用水（n = 1）处理锆（II）-C

  DOI：

  10.1039/dt9900001813
• 作为试剂：
  描述：

  间二甲苯 在 溴化锆(IV) 、 溶剂黄146 作用下， 以 水 为溶剂， 102.0~170.0 ℃ 、3.0 MPa 条件下， 反应 5.5h， 以450 g的产率得到间苯二甲酸
  参考文献：
  名称：

  산화반응 효율이 개선된 코발트/망간/브롬(Cobalt/Manganese/Bromide, CMB) 촉매계를 이용한 방향족 디카복실산의 제조방법

  摘要：

  本发明涉及一种在存在CMB（钴/锰/溴）催化剂体系下将二甲苯氧化制备芳香族二羧酸，例如异苯二甲酸的工艺中，通过向从CMB催化剂体系中回收的催化剂成分的活化过程中的氧化反应混合液（母液）中添加锆溴化物作为溴前体，以提高催化剂的氧化反应效率的方法。

  公开号：

  KR20200064512A

文献信息

• Regioselective addition of C(sp³)–H bonds of alkyl pyridines to olefins catalysed by cationic zirconium complexes
  作者：Qiu Sun、Peipei Xie、Dan Yuan、Yuanzhi Xia、Yingming Yao

  DOI：10.1039/c7cc03263c

  日期：——

  In situ generated cationic zirconium complexes stabilized by amine-bridged bis(phenolato) ligands have been developed to catalyse C(sp3)–H addition of alkyl pyridines to olefins, which are the first examples of group 4 metal based catalysts in this transformation. Ligand-controlled regioselectivity was observed, which was verified by DFT study.

  通过胺桥双（酚基）配体稳定化的原位生成的阳离子锆络合物已经被开发出来，可以催化烷基吡啶的C（sp 3）-H加成反应到烯烃中，这是该转化中第4类金属基催化剂的第一个例子。观察到配体控制的区域选择性，这通过DFT研究证实。
• 一种含IVB族金属的配合物、制备方法与应用
  申请人：万华化学集团股份有限公司

  公开号：CN111848662B

  公开（公告）日：2022-08-05

  本发明提供了一种含IVB族金属的配合物、制备方法与应用。一种含IVB族金属的配合物，其特征在于，具有下式所示的结构表达式：其中，R1–R5各自独立地选自氢、卤素或下列基团中的任意一种：C1‑6烷基、C1‑6烷氧基、C3‑10环烷基、C3‑10环烷基氧基、C6‑14芳基、C6‑14芳基氧基；M选自IVB族金属；X选自卤素、甲基、乙基、苄基、二甲基氨基或二乙基氨基。本发明制备的配合物在应用于烯烃聚合尤其是烯烃/α‑烯烃共聚时不仅具有较高的催化活性，而且热稳定性好，更适用于高温聚合反应体系。
• Attempts to prepare alkylidene zirconium complexes by α-hydrogen atom abstraction
  作者：Jeffrey H Wengrovius、Richard R Schrock

  DOI：10.1016/s0022-328x(00)82434-1

  日期：1981.2

  We prepared several new neopentyl halide complexes of zirconium in order to test whether they could be induced to lose neopentane and give neopentylidene complexes by adding phosphorus or nitrogen donor ligands. ZrNp2X2 (X  Cl or Br) can be prepared in ether and isolated as a dietherate (an oil). It reacts with L (L  PMe3, PMe2Ph, NEt3, DMPE, TMEDA) to give ZrNp2X2L2. ZrNp3Cl can be prepared by adding

  我们制备了几种新的锆新戊基卤化物配合物，以测试是否可以通过添加磷或氮供体配体来诱导它们失去新戊烷并生成新亚戊二烯配合物。ZrNp 2 X 2（XCl或Br）可以在乙醚中制备，并以二醚酸酯（油）的形式分离。它与L（LPMe 3，PMe 2 Ph，NEt 3，DMPE，TMEDA）反应生成ZrNp 2 X 2 L 2。ZrNp 3 Cl可以通过向ZrNp 2 Cl 2（醚）2中添加MgNp 2来制备并通过升华分离，产率为25％。在添加PMe 3或TMEDA时，它歧化为ZrNp 4和ZrNp 2 Cl 2 L 2。ZrCP“NPCL 2（CP”=η 5 -C 5我5），ZrCP“NP 2 Cl和ZrCP”NP 3通过添加MgNp制备2至ZrCP“CL 3。只有最后一个是固体，只有第一个形成加合物ZrCP''NPCl 2（PMe 3）。ZrNp 2 Cl 2（PMe 3）的光解没有化合物在L的
• Enthalpies of formation of alkali-metal hexabromo-zirconate, -hafnate, and -stannate
  作者：Ramesh Makhija、Alan D. Wastland

  DOI：10.1039/dt9770001707

  日期：——

  Enthalpies of reaction have been determined by solution calorimetry for the process (i) where M′2M = K2Zr, Cs2Zr, Cs2Hf, or K2Sn. The data lead to the following standard enthalpies of formation, ΔHf⊖(298 K): K2[ZrBr6], 2M′Br(c)+ MBr4(c)→ M′2[MBr6](c)(i)–1 603; Cs2[ZrBr6], –1 665; Cs2[HfBr6], –1 793; and K2[SnBr6], –1 214 kJ mol–1. The halide-ion affinities of the gaseous MBr4 and MCl4 molecules have

  反应焓已经通过溶液量热法的过程中所确定（i）在M' 2 M =ķ 2的Zr，铯2的Zr，铯2 HF，或K 2 Sn等。数据导致形成的下列标准焓Δ ħ ˚F ⊖（298 K）：K 2 [ZrBr 6 ]，2M'Br（C）+ MBR 4（c）中→ M' 2 [MBR 6 ]（c）中（i）–1603；Cs 2 [ZrBr 6 ]，– 1 665；Cs 2 [HfBr 6 ]，– 1 793；和K 2 [SnBr 6 ]，– 1 214 kJ mol –1。气态MBr 4和MCl 4分子的卤离子亲和力已经通过假设络合物的晶格能的半经验值进行了计算。卤化锡对卤化物的亲和力显着低于锆和ha卤化物。四溴化for对溴化物具有异常高的亲和力。在这方面，它与卤化锆有很大不同。
• Heavier halides of early transition elements by halide-exchange reactions. Crystal and molecular structure of [Ph3C]2[Hf2Cl10]
  作者：Fausto Calderazzo、Piersandro Pallavicini、Guido Pampaloni、Pier Francesco Zanazzi

  DOI：10.1039/dt9900002743

  日期：——

  The decahalogenodimetalates of zirconium(IV) and hafnium(IV) as their triphenylmethyl derivatives [Ph3C]2[M2Cl10] have been obtained by the reaction of M(BH4)4 with the appropriate Ph3CX or by addition of Ph3CX to MX4. The crystal and molecular structure of [Ph3C]2[Hf2Cl10] has been studied by X-ray diffraction methods: triclinic, space group P, a= 15.965(3), b= 12.907(3), c= 10.526(3)Å, α= 99.75(2)

  锆（的decahalogenodimetalates IV）和铪（IV）作为它们的三苯甲基衍生物[PH 3 C] 2 [M 2氯10 ]已经由M（BH反应得到4）4与适宜的pH 3 CX或通过加入Ph 3 CX转换为MX 4的过程。[ X 3 C] 2 [Hf 2 Cl 10 ]的晶体和分子结构已通过X射线衍射方法研究：三斜晶系，空间群P，a = 15.965（3），b= 12.907（3），c = 10.526（3）Å，α= 99.75（2），β= 84.84（2），γ= 102.64（2）°，Z =2。该结构由[Ph 3 C]组成+阳离子和[Hf 2 Cl 10 ] 2-阴离子，后者具有晶体对称性。氯化物桥接的二聚体具有扭曲的八面体配位，而[Ph 3 C] +阳离子在中心碳周围具有三角平面的几何形状。铌（V）和钽（V）的卤化物较重，是通过与Pr i Br进行交换反应从氯化物制备的（对于NbBr