五羰基溴铼(I) | 14220-21-4

• 物质功能分类: 有机原料 - 有机金属类化合物 - 有机铋、钴、镨、钆、镓、铱、铼、钇、铽等
• 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: 五羰基溴铼(I)
• 中文别名: 溴代五羰基铼；溴代五羰基铼(I)；五羰基溴化铼(I)
• 英文名称: bromopentacarbonylrhenium
• 英文别名: bromopentacarbonylrhenium(I)；Re(CO)5Br；ReBr(CO)5；pentacarbonyl rhenium bromide；rhenium(I) pentacarbonyl bromide；rhenium pentacarbonyl bromide；pentacarbonylbromorhenium；BrRe(CO)5；Bromorhenium;carbon monoxide
• CAS: 14220-21-4
• 化学式: C₅BrO₅Re
• 分子量: 406.163
• InChiKey: NWJBOTGGBYFKEJ-UHFFFAOYSA-M

物化性质

• 熔点：
  90°C (subl.)
• 稳定性/保质期：

  在常温常压下稳定，应避免与以下物质接触：

  • 水分/潮湿
  • 氧化物
  • 卤素

计算性质

• 辛醇/水分配系数(LogP)：
  0.66
• 重原子数：
  12
• 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：
  5
• 氢给体数：
  0
• 氢受体数：
  5

ADMET

代谢

溴主要通过吸入进入人体，但也可以通过皮肤接触。溴盐可以摄入。由于溴的活性，它会迅速形成溴化物并可能沉积在组织中，取代其他卤素。

Bromine is mainly absorbed via inhalation, but may also enter the body through dermal contact. Bromine salts can be ingested. Due to its reactivity, bromine quickly forms bromide and may be deposited in the tissues, displacing other halogens. (L626)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

溴是一种强大的氧化剂，能够从粘膜的水分中释放出氧自由基。这些自由基也是有力的氧化剂，能够造成组织损伤。此外，氢溴酸和溴酸的形成将导致二次刺激。溴离子还已知会影响中枢神经系统，导致溴中毒。这被认为是溴离子取代神经递质和传输系统中的氯离子的结果，从而影响许多突触过程。（L626, L627, A543）

Bromine is a powerful oxidizing agent and is able to release oxygen free radicals from the water in mucous membranes. These free radicals are also potent oxidizers and produce tissue damage. In additon, the formation of hydrobromic and bromic acids will result in secondary irritation. The bromide ion is also known to affect the central nervous system, causing bromism. This is believed to be a result of bromide ions substituting for chloride ions in the in actions of neurotransmitters and transport systems, thus affecting numerous synaptic processes. (L626, L627, A543)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌物分类

对人类不具有致癌性（未被国际癌症研究机构IARC列名）。

No indication of carcinogenicity to humans (not listed by IARC).

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

溴蒸气会引起刺激和对粘膜的直接损害。元素溴也会烧伤皮肤。溴化物离子是一种中枢神经系统抑制剂，长期暴露会产生神经元效应。这被称为溴中毒，可能导致从中睡意到昏迷、恶病质、昏迷、反射丧失或病理反射、阵挛性癫痫、震颤、共济失调、神经敏感性丧失、瘫痪、眼乳头水肿、言语异常、脑水肿、谵妄、攻击性和精神病的中心反应。

Bromine vapour causes irritation and direct damage to the mucous membranes. Elemental bromine also burns the skin. The bromide ion is a central nervous system depressant and chronic exposure produces neuronal effects. This is called bromism and can result in central reactions reaching from somnolence to coma, cachexia, exicosis, loss of reflexes or pathologic reflexes, clonic seizures, tremor, ataxia, loss of neural sensitivity, paresis, papillar edema of the eyes, abnormal speech, cerebral edema, delirium, aggressiveness, and psychoses. (L625, L626, L627)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 暴露途径

口服（L626）；吸入（L626）；皮肤给药（L626）

Oral (L626) ; inhalation (L626) ; dermal (L626)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 症状

溴蒸气会引起刺激和对粘膜的直接损害。症状包括流泪、流鼻涕、眼部刺激伴有来自咽和上呼吸道的粘液分泌、咳嗽、呼吸困难、窒息、喘息、鼻出血和头痛。溴离子是一种中枢神经系统抑制剂，会引起共济失调、言语不清、震颤、恶心、呕吐、乏力、眩晕、视觉障碍、不稳、头痛、记忆和注意力受损、定向障碍和幻觉。这被称为溴中毒。

Bromine vapour causes irritation and direct damage to the mucous membranes. Symptoms include lacrimation, rhinorrhoea, eye irritation with mucous secretions from the oropharyngeal and upper airways, coughing, dyspnoea, choking, wheezing, epistaxis, and headache. The bromide ion is a central nervous system depressant producing ataxia, slurred speech, tremor, nausea, vomiting, lethargy, dizziness, visual disturbances, unsteadiness, headaches, impaired memory and concentration, disorientation and hallucinations. This is called bromism. (L626, L627)

来源:Toxin and Toxin Target Database (T3DB)

安全信息

• 危险等级：
  6.1
• 危险品标志：
  Xn,T
• 安全说明：
  S26,S28,S36/37,S36/37/39,S45
• 危险类别码：
  R23/24/25,R20/21/22,R36/37/38
• WGK Germany：
  3
• 海关编码：
  29310099
• 包装等级：
  II
• 危险类别：
  6.1
• 危险品运输编号：
  UN 3288 6
• 储存条件：
  请将产品存放在常温下，密闭避光，保持通风和干燥环境。

SDS

Name:	Rhenium pentacarbonyl bromide Material Safety Data Sheet
Synonym:	Bromopentacarbonylrheniu
CAS:	14220-21-4

Section 1 - Chemical Product MSDS Name:Rhenium pentacarbonyl bromide Material Safety Data Sheet
Synonym:Bromopentacarbonylrheniu

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
14220-21-4	Rhenium pentacarbonyl bromide		238-084-8

Hazard Symbols: XN
Risk Phrases: 20/21/22

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Harmful by inhalation, in contact with skin and if swallowed.Air sensitive.Moisture sensitive.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation. Harmful if absorbed through the skin.
Ingestion:
Harmful if swallowed. May cause irritation of the digestive tract.
Inhalation:
Harmful if inhaled. May cause respiratory tract irritation.
Chronic:
Not available.

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Section 4 - FIRST AID MEASURES
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes.
Ingestion:
Get medical aid. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:

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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.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical 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.

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Section 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes.
Storage:
Store in a cool, dry place. Store in a tightly closed container.
Store under nitrogen.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 14220-21-4: 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: Crystals
Color: off-white
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: Insoluble.
Specific Gravity/Density:
Molecular Formula: C5BrO5Re
Molecular Weight: 406.16

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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:
Oxidizing agents, halogens, active metals.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide, hydrogen bromide.
Hazardous Polymerization: Will not occur.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 14220-21-4 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Rhenium pentacarbonyl bromide - 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: TOXIC SOLID, ORGANIC, N.O.S.*
Hazard Class: 6.1
UN Number: 2811
Packing Group: III
IMO
Shipping Name: TOXIC SOLID, ORGANIC, N.O.S.
Hazard Class: 6.1
UN Number: 2811
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: XN
Risk Phrases:
R 20/21/22 Harmful by inhalation, in contact with
skin and if swallowed.
Safety Phrases:
S 36/37 Wear suitable protective clothing and
gloves.
WGK (Water Danger/Protection)
CAS# 14220-21-4: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 14220-21-4 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 14220-21-4 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  五羰基溴铼(I) 以 四氢呋喃 、 甲基环己烷 为溶剂， 生成 十羰基二铼
  参考文献：
  名称：

  Young, Kent M.; Miller, Timothy M.; Wrighton, Mark S., Journal of the American Chemical Society, 1990, vol. 112, # 4, p. 1529 - 1537

  摘要：

  DOI：
• 作为产物：
  描述：

  五羰基氯铼(I) 在 C₆H₅CH₂Br 作用下， 以 四氢呋喃 、 甲基环己烷 为溶剂， 生成 五羰基溴铼(I)
  参考文献：
  名称：

  Young, Kent M.; Miller, Timothy M.; Wrighton, Mark S., Journal of the American Chemical Society, 1990, vol. 112, # 4, p. 1529 - 1537

  摘要：

  DOI：
• 作为试剂：
  描述：

  4-甲氧基苄醇 在 五羰基溴铼(I) 、 三苯基硅烷 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 5.0h， 以33%的产率得到对甲苯甲醚
  参考文献：
  名称：

  铼络合物催化的氢硅烷脱氧和醇甲硅烷基化

  摘要：

  铼配合物（如 ReBr(CO) 5 ）有效地催化苯甲基、叔和烯丙醇与氢硅烷的还原反应，以中等至良好的收率得到相应的脱氧产物烷烃。在脂肪族仲醇的情况下，烷烃随着脱水产物的形成而形成。另一方面，在伯醇和环状醇的情况下，醇的甲硅烷基化继续形成相应的甲硅烷基醚。

  DOI：

  10.1016/j.tetlet.2022.153839

文献信息

• Synthesis of a Novel Re(I)-Ru(II)-Re(I) Trinuclear Complex as an Effective Photocatalyst for CO₂ Reduction
  作者：Akinari Umemoto、Yasuomi Yamazaki、Daiki Saito、Yusuke Tamaki、Osamu Ishitani

  DOI：10.1246/bcsj.20190284

  日期：2020.1.15

  Supramolecular photocatalysts, which consist of redox photosensitizer and catalyst units, have recently attracted attention in the field of artificial photosynthesis. Aiming to construct a durable supramolecular photocatalyst for CO2 reduction, a new Re–Ru–Re trinuclear complex was successfully developed, where one Ru unit, acting as photosensitizer, was linked to two Re units, acting as catalysts, through ethylene chains. The novel complex was synthesized by creating two chelate moieties on the ligand of a Ru complex using the Negishi-coupling reaction, which were then coordinated to Re complexes. This trinuclear complex selectively photocatalyzed the reduction of CO2 to CO under visible light irradiation, with high durability compared with the corresponding Ru–Re binuclear complex and a mixed system of model mononuclear complexes. Absorption spectra and mass spectroscopic data of the reaction solutions revealed a rapid consumption of the electrons on the one-electron reduced species of the Ru unit, which led to suppression of the Ru unit decomposition, thereby maintaining its photosensitizing ability and product selectivity.

  超分子光催化剂由氧化还原光敏剂和催化单元组成，在人工光合作用领域近期受到了关注。为了构建用于CO2还原的长效超分子光催化剂，成功开发了一种新型Re–Ru–Re三核络合物，其中一个作为光敏剂的Ru单元通过乙烯链连接到两个作为催化剂的Re单元。这一新颖的络合物通过Negishi偶联反应在Ru络合物的配体上创建了两个螯合基团，随后与Re络合物结合而合成。该三核络合物在可见光照射下选择性光催化 还原为CO，相比于相应的Ru–Re双核络合物和单核络合物模型混合体系，具有更高的耐久性。反应溶液的吸收光谱和质谱数据显示，Ru单元的一电子还原物种上的电子迅速消耗，导致Ru单元的分解受到抑制，从而维持了其光敏化能力和产品选择性。
• Novel rhenium(i) catalysts for the isomerization of propargylic alcohols into α,β-unsaturated carbonyl compounds: an unprecedented recyclable catalytic system in ionic liquids
  作者：Joaquín García-Álvarez、Josefina Díez、José Gimeno、Christine M. Seifried

  DOI：10.1039/c1cc10768b

  日期：——

  Carbonyl rhenium(I) complexes are efficient catalysts for the regioselective isomerization of terminal propargylic alcohols into α,β-unsaturated aldehydes or ketones which can be used as an unprecedented recyclable catalytic system (up to 10 consecutive runs) in the ionic liquid [BMIM][PF6].

  羰基铼(I)配合物作为催化剂，能够高效地选择性异构化末端炔丙醇为α,β-不饱和醛或酮，这种催化体系前所未有地可在离子液体[BMIM][PF6]中循环使用（多达10次连续运行）。
• (8-Amino)quinoline and (4-amino)phenanthridine complexes of Re(CO)3 halides
  作者：Sanjay Gaire、Robert J. Ortiz、Briana R. Schrage、Issiah B. Lozada、Pavan Mandapati、Allen J. Osinski、David E. Herbert、Christopher J. Ziegler

  DOI：10.1016/j.jorganchem.2020.121338

  日期：2020.8

  present a study on the synthesis, structure and electronics of a series of (8-amino)quinoline and (4-amino)phenanthridine complexes of Re(CO)3X, where X = Cl and Br. In all cases, the (amino)heterocycles bind as bidentate ligands, with surprisingly symmetric modes of binding based on Re–N bond lengths. Between the complexes of (8-amino)quinolines and (4-amino)phenanthridines studied in this report, we do

  在本报告中，我们对 Re(CO) 3 X的一系列（8-氨基）喹啉和（4-氨基）菲啶配合物的合成、结构和电子学进行了研究，其中 X = Cl 和 Br。在所有情况下，（氨基）杂环作为双齿配体结合，具有基于 Re-N 键长的令人惊讶的对称结合模式。在本报告中研究的（8-氨基）喹啉和（4-氨基）菲啶的复合物之间，我们没有观察到太多的结构变化和非常相似的紫外-可见吸收光谱。(4-氨基)菲啶复合物中 π 系统的扩展确实导致最低能量跃迁强度的增加 ( λ max)，计算模型表明，与较小的 (8-氨基) 喹啉支持的复合物中这些跃迁的混合 π-π∗/MLCT 特征相比，其更纯粹的 MLCT 特征。DFT 和 TDDFT 建模进一步表明，考虑自旋轨道耦合 (SOC) 是必不可少的；省略 SOC 会错过 π-π∗ 对λ max 的贡献，并且无法准确模拟观察到的电子吸收光谱。
• Using hydrazine to link ferrocene with Re(CO)3: A modular approach
  作者：Kullapa Chanawanno、Hannah M. Rhoda、Abed Hasheminasab、Laura A. Crandall、Alexander J. King、Richard S. Herrick、Victor N. Nemykin、Christopher J. Ziegler

  DOI：10.1016/j.jorganchem.2016.06.004

  日期：2016.9

  Acetyl ferrocene and diacetyl ferrocene both readily react with an excess of hydrazine to afford the corresponding hydrazone compounds. These compounds can then be linked to Re(CO)3 via a metal-mediated Schiff base reaction, resulting in a series of ferrocene-Re(CO)3 conjugates with different stoichiometries. Conjugates with 1:1, 1:2, and 2:1 ferrocene: Re(CO)3 ratios can be produced via this "modular"

  乙酰基二茂铁和二乙酰基二茂铁都容易与过量的肼反应，得到相应的化合物。然后，这些化合物可以通过金属介导的席夫碱反应与Re（CO）3连接，产生一系列具有不同化学计量比的二茂铁-Re（CO）3共轭物。可以通过这种“模块化”类型的合成方法产生二茂铁：Re（CO）3比为1：1、1：2和2：1的共轭物。这些缀合物的几个例子进行了结构表征，并研究了它们的光谱，电化学和光谱电化学行为。还使用DFT和TDDFT计算来探测这些化合物的电子结构。
• Capturing Re(<scp>i</scp>) in an neutral N,N,N pincer Scaffold and resulting enhanced absorption of visible light
  作者：Philip Bulsink、Ahlam Al-Ghamdi、Prajesh Joshi、Ilia Korobkov、Tom Woo、Darrin Richeson

  DOI：10.1039/c6dt00661b

  日期：——

  (κ3-terpy)Re(CO)2X (X = Cl, Br). The synthesis, single crystal X-ray structural and spectroscopic characterization of these eight species documents their Re coordination geometries and demonstrates the accessibility of such compounds. The basic photophysical features of these compounds show significant elaboration in both number and intensity of the d–π* transitions observed in the UV-vis spectra relative to the

  largely （I）的有机金属和配位化学在很大程度上仅限于二齿α-二亚胺的连接和面部三羰基配位的几何形状。二齿二（亚氨基）吡啶和双齿三联吡啶络合物在氮气氛下的热转化在200-240℃下导致了家庭的Re（的我）钳形络合物[κ 3 -2,6- ARN CME} 2（NC 5 ħ 3）] Re（CO）2 X（Ar C 6 H 5，Me 2 C 6 H 3，i Pr 2 C 6 H3；X =氯，溴）和（κ 3 -terpy）的Re（CO） 2 X（X =氯，溴）。这八个物种的合成，单晶X射线结构和光谱表征证明了它们的Re配位几何形状，并证明了此类化合物的可及性。这些化合物的基本光物理特征表明，相对于二齿原料，在紫外可见光谱中观察到的d–π *跃迁的数量和强度都得到了很好的阐述，并使用了随时间变化的DFT计算对这些光谱进行了分析。