四氧化钌 | 20427-56-9

• 物质功能分类: 无机化工 - 氧化物和过氧化物 - 金属氧化物
• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 过渡金属有机体
• 中文名称: 四氧化钌
• 中文别名: 氧化钌
• 英文名称: ruthenium tetroxide
• 英文别名: tetraoxoruthenium
• CAS: 20427-56-9
• 化学式: O₄Ru
• 分子量: 165.068
• InChiKey: GJFMDWMEOCWXGJ-UHFFFAOYSA-N

物化性质

• 熔点：
  25.4°
• 沸点：
  bp 40°
• 密度：
  3.290
• 溶解度：
  微溶于H2O；极易溶于四氯化碳；反应乙醇
• 稳定性/保质期：
  四氧化钌是一种非常危险的试剂，能够与滤纸和醇发生爆炸性反应，与醚、苯和吡啶的反应也非常剧烈。它容易氧化人体内的组织，留下二氧化钌沉积，并且其蒸气能强烈刺激眼睛和呼吸道，因此使用时一定要避免吸入。但在反应中仅使用催化剂量的四氧化钌时，这些危险性能显著降低。

计算性质

• 辛醇/水分配系数(LogP)：
  -0.48
• 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：
  68.3
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险等级：
  5.1
• 安全说明：
  S16,S17,S36,S37,S39
• 海关编码：
  28439000
• 危险品运输编号：
  UN 3139
• 包装等级：
  I
• 危险类别：
  5.1

SDS

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Section 1: Product Identification
Chemical Name: Ruthenium(VIII) oxide (0.5% stabilized aqueous solution)
CAS Registry Number: 20427-56-9
Formula: RuO4
EINECS Number: none
Chemical Family: metal oxide
Synonym: ruthenium tetroxide

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title Compound 20427-56-9 0.5% no data no data

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin, eyes and mucous membranes. May be harmful if swallowed.
Primary Routes of Exposure: Ingestion, eyes
Eye Contact: Causes slight to mild irritation of the eyes.
Skin Contact: Causes slight to mild irritation of the skin.
Inhalation: Irritating 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: Exposure to ruthenium tetroxide dust and vapors may cause severe permanent damage to eyes and lungs.
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
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: not applicable
Autoignition Temperature: not applicable
Explosion Limits: not applicable
Extinguishing Medium: Aqueous solution - non-flammable
When dry acts as an oxidizer towards organics. Smothering the fire may not be effective. A NIOSH approved
Special Fire Fighting Procedures:
self contained breathing apparatus should be worn.
Hazardous Combustion and Toxic ruthenium tetroxide could be present in gasses.
Decomposion Products:
Wetting the dried solid with small amounts of alcohols, solvents or combustible powders may lead to ignition
Unusual Fire or Explosion Hazards:
and fire.

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SECTION 6: Accidental Release Measures
Small spills should be flushed with sodium bisulfite solution to detoxify ruthenium tetroxide, and then be mixed
Spill and Leak Procedures:
with vermiculite or sodium carbonate and swept up. Do not mix with combustible materials.

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SECTION 7: Handling and Storage
Handling and Storage: Store in a cool dark place in tightly closed containers.

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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 appropriate chemical resistant gloves and protective clothing.
Ventilation: Material may form a fine dust or vapor. 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 Respirator
Respirator:
Protection Program to be in compliance with 29 CFR 1910.134.
Ventilation: Material may form a fine dust or vapor. 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: yellow liq.
Molecular Weight: 165.7
Melting Point: no data
Boiling Point: (water)
Vapor Pressure: no data
Specific Gravity: no data
Odor: acrid odor
Solubility in Water: material is a water solution

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SECTION 10: Stability and Reactivity
Stability: heat sensitive, (store cold, in the dark)
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: The dry powder reacts violently with paper, alcohol, and other combustibles.
Incompatibility: Reducing agents, organic materials, active metals and halogens
Decomposition Products: ruthenium and oxygen

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SECTION 11: Toxicological Information
RTECS Data: No information available in the RTECS files.
Carcinogenic Effects: No data available
Mutagenic Effects: No data available
Tetratogenic Effects: No data available

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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): Oxidizing liquid, N.O.S.
Hazard Class (CFR): 5.1
Additional Hazard Class (CFR): NA
Packaging Group (CFR): II
UN ID Number (CFR): UN# 3139
Shipping Name (IATA): Oxidizing liquid, N.O.S.
Hazard Class (IATA): 5.1
Additional Hazard Class (IATA): NA
Packaging Group (IATA): II
UN ID Number (IATA): UN# 3139

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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

制备方法与用途

化学性质

这是一种深蓝色四方晶系结晶粉末，相对密度为6.97。它溶于熔融碱溶液，生成Na2RuO4，不溶于水和酸。加热至1025℃时不会发生变化，在1400℃以上开始分解并部分汽化。在氢气流中加热则会还原生成金属钌。

用途

该物质主要用于电子工业中的厚膜电阻、电位器等元件的制造。

生产方法

可以通过将粉末状金属钌在800～900℃的氧气中加热1小时，或者将钌的硫化物、硫酸盐或氯化物在空气中或氧气中灼烧来制备二氧化钌成品。

反应信息

• 作为反应物：
  描述：

  四氧化钌 在 hydroxide 作用下， 以 水 为溶剂， 生成 ruthenate(VI)(2-)
  参考文献：
  名称：

  二氧化钌水合物与铈（IV）水溶液的反应和催化性能

  摘要：

  使用Ce 4+在0.5 mol dm –3 H 2 SO 4中的测试系统研究了水合二氧化钌（RuO 2 · x H 2 O）的氧化还原催化性能。粉末形式的RuO 2 · x H 2 O除非与惰性载体（如二氧化钛（TiO 2））结合，否则表现出不良的氧化还原催化剂。这归因于四氧化钌（RuO 4）的产生，这是通过RuO 2 · x H 2 O和RuO 2 · x H 2观察到的。O–TiO 2混合物，但不与TiO 2结合的RuO 2催化剂一起使用。在没有催化剂的情况下，或使用TiO 2或Al 2 O 3时，未观察到Ce 4+的衰减（t > 200 h）。

  DOI：

  10.1039/dt9820001213
• 作为产物：
  描述：

  ruthenium(IV) oxide 以 not given 为溶剂， 生成 四氧化钌
  参考文献：
  名称：

  Baranaev, M. K.; Vereskunnov, V. G.; Zakharova, K. P., Atomnaya Energiya, 1964, vol. 17, p. 502 - 503

  摘要：

  DOI：
• 作为试剂：
  描述：

  1,2,2,6,6-五甲基哌啶 在 四氧化钌 作用下， 以 四氯化碳 为溶剂， 反应 2.0h， 以53%的产率得到2,2,6,6-四甲基哌啶-1-甲醛
  参考文献：
  名称：

  药物代谢的化学研究 II. 四氧化钌对某些脂环胺的 N-去甲基化和 N-氧化

  摘要：

  用四氧化钌氧化脂环族 N-甲胺，如哌啶 (1a)、9-甲基-9-氮杂双环 [3.3.1] 壬烷 (2a) 和 8-甲基-8-氮杂双环 [3.2.1] 辛烷 (3a) ，其中与氮连接的碳原子受到空间位阻，导致 N-甲酰基和 N-去甲基化衍生物。后者，当进一步氧化时，以良好的产率得到 N-氧化物。

  DOI：

  10.1002/ardp.19843170712

文献信息

• A new epoxidation catalyst: the reactivity and X-ray crystal structure of [RuO₂(bipy){IO₃(OH)₃}]·1.5H₂O (bipy = 2,2′-bipyridine)
  作者：Alan J. Bailey、William P. Griffith、Andrew J. P. White、David J. Williams

  DOI：10.1039/c39940001833

  日期：——

  The crystal structure of [RuO2(bipy)IO3(OH)3}]·1.5H2O 1 is reported: with NaIO4 or NBun4IO4 as cooxidant it is an efficient catalyst for alkene epoxidations under mild conditions; it also oxidises primary alcohols to aldehydes and secondary alcohols to ketones.

  报道了[RuO2(bipy)IO3(OH)3}]·1.5H2O 1的晶体结构：以NaIO4或NBun4IO4为共氧化剂，在温和条件下，它是一种高效的烯烃环氧化催化剂；同时，它还能将伯醇氧化为醛，将仲醇氧化为酮。
• Simple and complex oxyhalides of ruthenium and osmium
  作者：M.A. Hepworth、P.L. Robinson

  DOI：10.1016/0022-1902(57)80104-3

  日期：1957.2

  Attempts to prepare simple and complex oxyfluorides of ruthenium have failed. Osmium is shown to form an octavalent oxyfluoride, OsO3F2, the parent of the trifluoroperperosmates, MIOsO3F3 (MI = K, Cs, Ag). The preparation of an oxychloride of hexavalent osmium, OsOCl4, is also described together with its reaction with hydrochloric acid under varying conditions. Structural and magnetic data are presented

  制备简单和复杂的钌氟氧化物的尝试失败了。显示形成八价的氟氧化物OsO 3 F 2，即三氟过碘酸盐M I OsO 3 F 3的母体（M I = K，Cs，Ag）。还描述了六价的氧氯化物OsOCl 4的制备及其在不同条件下与盐酸的反应。给出了Cs 2 MO 2 Cl 4型化合物的结构和磁性数据（M = Ru，Os）。
• Studies on transition–metal oxo and nitrido complexes. Part 10. New oxo–ruthenium and oxo–osmium pyridine complexes, and use of the former as catalysts for oxidation of alcohols
  作者：Ahmed M. El-Hendawy、William P. Griffith、Fatma I. Taha、Mahmoud N. Moussa

  DOI：10.1039/dt9890000901

  日期：——

  The new complexes trans-[RuO2(py)4]2+, trans-[OsO2(py)3(H2O)]2+, trans-[MO2(py)2X2](M = Ru or Os; X = Cl or Br, py = pyridine) and trans-[Ru2O6(py)4] are reported. Both trans-[RuO2(py)4]2+ and trans-[Ru2O6(py)4] in CH2Cl2 are efficient oxidants for primary alcohols to aldehydes and secondary alcohols to ketones, and function catalytically, with N-methylmorpholine N-oxide (mmo) or [NBun4][IO4] as co-oxidants

  新的复合物反式-[RuO 2（py）4 ] 2+，反式-[OsO 2（py）3（H 2 O）] 2+，反式-[MO 2（py）2 X 2 ]（M = Ru或Os； X ＝ Cl或Br，py ＝吡啶）和反式-[Ru 2 O 6（py）4 ]。两个反式- [的RuO 2（PY）4 ] 2+和反式- [孺2 ö 6（PY）4CH 2 Cl 2中的]是伯醇转化为醛和仲醇转化为酮的有效氧化剂，并以N-甲基吗啉N-氧化物（mmo）或[NBu n 4 ] [IO 4 ]为助氧化剂起作用。反式-[Ru（py）4 Cl 2 ]的简单制备及[OsO 4 ·L]，[OsO 2 L 2（O 2 C 2 H 4）]和[OsO 2 L 2（O 2）的分离C 6高10）]（L ＝吡啶N-氧化物）也有报道。通过拉曼光谱，红外光谱和1 H核磁共振谱对复合物进行表征。
• Structural and Magnetic Studies of <i>AB</i>O₄-Type Ruthenium and Osmium Oxides
  作者：Sean Injac、Alexander K. L. Yuen、Maxim Avdeev、Chun-Hai Wang、Peter Turner、Helen E. A. Brand、Brendan J. Kennedy

  DOI：10.1021/acs.inorgchem.9b03118

  日期：2020.3.2

  both displayed discontinuous phase transitions to I41/a at high temperatures. CsOsO4 was determined to undergo a phase transition to a P21/c structure below 140 K. CsRuO4 crystallizes with a baryte-type structure at room temperature. Upon heating CsRuO4 a first order phase transition to the scheelite structure in I41/a is observed at 400 K. A continuous phase transition is observed to P212121 below

  合成了ABO4形式的氧化物，其中A = K，Rb，Cs和B = Ru和Os，并通过衍射和磁技术进行了表征。对于A = K，氧化物采用四方（I41 / a）白钨矿结构。RbOsO4在室温下结晶为白钨矿，在550 K附近经历连续相转变为I41 / amd。发现RbRuO4和CsOsO4在正交晶（Pnma）伪白钨矿结构中结晶，并且都显示出不连续的相转变为I41 / a。在高温下。确定CsOsO4在140 K以下发生相转变为P21 / c结构。CsRuO4在室温下以重晶石型结构结晶。加热CsRuO4后，在400 K下观察到I41 / a中白钨矿结构的一级相变。在140 K以下观察到P212121的连续相变。直流磁化率数据与所有化合物在低温下的远距离反铁磁排序一致，除了CsOsO4顺磁性为2K。有效磁矩与S = 1/2量子磁体的仅自旋值一致。计算出的Os化合物的有效磁矩低于Ru的对应磁矩，这反映了自
• Studies on transition-metal nitrido and oxo complexes. Part 14. Carboxylato oxo-osmium(VI) and -ruthenium(VI) complexes and their reactions
  作者：William P. Griffith、Jennifer M. Jolliffe

  DOI：10.1039/dt9920003483

  日期：——

  The new complexes [OsO2(OCOR)Cl2]–[R = Me, Et or CH(Me)Et] and [RuO2(OCOR)Cl2]–(R = Me, Et, Pr or CHF2) have been prepared. In addition to functioning as catalytic oxidants for organic substrates in the presence of N-methylmorpholine N-oxide as co-oxidant, the acetato complexes [MO2(OCOMe)Cl2]– in particular can be used as precursors for a wide variety of complexes. New species prepared from these

  新的络合物[OsO 2（OCOR）Cl 2 ] – [R = Me，Et或CH（Me）Et]和[RuO 2（OCOR）Cl 2 ] –（R = Me，Et，Pr或CHF 2）具有准备好了。除了在N-甲基吗啉N-氧化物作为共氧化剂的情况下用作有机底物的催化氧化剂外，乙酰复合物[MO 2（OCOMe）Cl 2 ] –特别是可以用作多种化合物的前体复合体。由此制备的新物种包括[OsO 2（NCO）4 ] 2–，[OsO 2（SCN）4 ] 2–，[OsO 2（acac）Cl 2 ] –（acac =戊烷-2,4-二酸酯），[Os（terpy）Cl 3 ] +（terpy = 2,2'：6'， 2″-叔吡啶），[OsO 2（S 2 CNEt 2）2 ]和[Ru（OH）（H 2 O）（O 2 COCR 1 R 2）Cl 2 ]（R 1＝ R 2＝ Me或Et； R 1 = Me，R 2 = Et或Ph）。