十二羰基三锇 | 15696-40-9

• 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: 有机化合物 - 有机盐 - 有机金属盐
• 中文名称: 十二羰基三锇
• 中文别名: 羰基钛
• 英文名称: dodecacarbonyl triosmium
• 英文别名: Os₃(CO)₁₂；triosmium dodecacarbonyl；Carbon monoxide;osmium；carbon monoxide;osmium
• CAS: 15696-40-9
• 化学式: C₁₂O₁₂Os₃
• 分子量: 906.725
• InChiKey: VUBLMKVEIPBYME-UHFFFAOYSA-N

物化性质

• 熔点：
  224 °C(lit.)
• 密度：
  3,48 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  -0.46
• 重原子数：
  27
• 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：
  12
• 氢给体数：
  0
• 氢受体数：
  12

安全信息

• 危险等级：
  6.1
• 危险品标志：
  Xn
• 安全说明：
  S22,S26,S36/37/39
• 危险类别码：
  R22,R36/37/38
• WGK Germany：
  3
• 海关编码：
  28439090
• 包装等级：
  II
• 危险类别：
  6.1
• 危险品运输编号：
  UN 3466
• 危险标志：
  GHS07
• 危险性描述：
  H302,H315,H319,H335
• 危险性防范说明：
  P261,P305 + P351 + P338

SDS

Name:	Triosmium Dodecacarbonyl 98% Material Safety Data Sheet
Synonym:	None
CAS:	15696-40-9

Section 1 - Chemical Product MSDS Name:Triosmium Dodecacarbonyl 98% Material Safety Data Sheet
Synonym:None

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
15696-40-9	Triosmium Dodecacarbonyl	98%	239-789-3

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.The toxicological properties of this material have not been fully investigated.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation.
Ingestion:
May cause irritation of the digestive tract. The toxicological properties of this substance have not been fully investigated.
Inhalation:
May cause respiratory tract irritation. The toxicological properties of this substance have not been fully investigated.
Chronic:
No information found.

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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. Wash clothing before reuse.
Ingestion:
Get medical aid. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or 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. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion.
Extinguishing Media:
Use agent most appropriate to extinguish fire. Use water spray, dry chemical, carbon dioxide, 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. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Use with adequate ventilation.
Minimize dust generation and accumulation. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation.
Storage:
Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances.

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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# 15696-40-9: Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI Z88.2 requirements or European Standard EN 149 must be followed whenever workplace conditions warrant respirator use.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Crystalline powder
Color: yellow crystalline powder
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 224 deg C
Autoignition Temperature: Not applicable.
Flash Point: Not applicable.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C12O12Os3
Molecular Weight: 906.73

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable at room temperature in closed containers under normal storage and handling conditions.
Conditions to Avoid:
Incompatible materials, dust generation, excess heat.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 15696-40-9 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Triosmium Dodecacarbonyl - 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: METAL CARBONYLS, N.O.S.*
Hazard Class: 6.1
UN Number: 3281
Packing Group: III
IMO
Shipping Name: METAL CARBONYLS, N.O.S.
Hazard Class: 6.1
UN Number: 3281
Packing Group: III
RID/ADR
Shipping Name: METAL CARBONYLS, N.O.S.
Hazard Class: 6.1
UN Number: 3281
Packing group: III

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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 28A After contact with skin, wash immediately with
plenty of water.
S 36/37 Wear suitable protective clothing and
gloves.
S 37 Wear suitable gloves.
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# 15696-40-9: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 15696-40-9 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 15696-40-9 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：

  十二羰基三锇 在 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 以35%的产率得到Os₃(CO)₁₁(PPh₃)
  参考文献：
  名称：

  有机金属簇中的电子转移：十一。M 3（CO）12（M = Ru，Os）和PPh 3衍生物的氧化还原化学；亲核取代的催化机理

  摘要：

  对于所有溶剂中的M 3（CO）12和M 3（CO）12 - n（PPh 3）n（M = Ru，Os）团簇，已经建立了涉及一种机理的双电子还原过程的一般性。CH 2 Cl 2中的详细电量分析和光谱研究为形成“开放的” M 3（CO）12 2-物种（半衰期小于10的三自由基自由基阴离子M 3（CO）12- ·）提供了有力证据。CH 2 Cl 2中的-6 s。然而，电化学反应对水的存在敏感并且是浓度依赖性的。仅在<5×10 -4 mol dm -3的低浓度下和在干燥箱条件下才能检测到“开放”的M 3（CO）12 2-的电化学响应。通过对这些阴离子在CH 2 Cl 2中的电化学研究，证实了在较高浓度下和存在水M 3（CO）11 2-和M 6（CO）18 2-的条件下研磨的电活性物质。HM 3（CO）11 -不是一个产品。夫妻[M6（CO）18 ] - / 2-是在一定条件下但HM的氧化化学可逆3（CO）11

  DOI：

  10.1016/0022-328x(87)85060-x
• 作为产物：
  描述：

  四氧化锇 在 carbon monoxide 作用下， 以 苯 为溶剂， 生成 十二羰基三锇
  参考文献：
  名称：

  非均相加氢脱氮催化剂中含氮杂环与活性催化剂位点相互作用的潜在模型

  摘要：

  DOI：

  10.1021/om00130a018
• 作为试剂：
  描述：

  一氧化碳 、 4-乙烯基-1-环己烯 在 十二羰基三锇 、 2-(dicyclohexylphosphanyl)-1-(2-methoxyphenyl)-1H-imidazole 、 氢气 作用下， 以 乙腈 为溶剂， 130.0 ℃ 、6.0 MPa 条件下， 反应 20.0h， 生成 3-(3-环己烯基)丙醛
  参考文献：
  名称：

  Highly regioselective osmium-catalyzed hydroformylation

  摘要：

  铂酸酯与2-咪唑基取代膦配体结合形成活性物种，用于高度区域选择性和通用烯烃水合甲酰化反应，产生良好产率和优异区域选择性的醛类产物。获得了一种不寻常的磷配体桥联的三核铂催化剂结构。

  DOI：

  10.1039/c4cc05626d

文献信息

• The photochemical generation of heterobimetallic complexes containing carbon disulfide
  作者：Peter V. Broadhurst、Nicholas E. Leadbeater、Jack Lewis、Paul R. Raithby

  DOI：10.1039/a704141a

  日期：——

  [Fe(CO)2(PR3)2(η2-CS2)] leads to [(PR3)2(CO)2Fe(µ-η2∶η1-CS2)Os3(CO)11]. Photolysis of a thf solution of (PEt3)2(CO)2Fe(µ-η2∶η1-CS2)M(CO)5] with PEt3 results in the formation of the phosphine-substituted complex [(PPh3)2(CO)2Fe(µ-η2∶η1-CS2)M(CO)4(PEt3)]. Single-crystal X-ray diffraction has been used to determine the molecular structures of [(PPh3)2(CO)2Fe(µ-η2∶η1-CS2)W(CO)5], [(PEt3)2(CO)2Fe(µ-η2∶η1-CS2)Os3(CO)11]

  光化学已用于产生许多含有π+σCS 2桥基的杂双金属配合物。的四氢呋喃（THF宽频带紫外光解[M（CO）的溶液）6用的[Fe（CO）]（M =的Cr，Mo或W）2（PR 3）2（η 2 -CS 2）]（R =的Et或pH）导致形成双金属配合物[（PR 3）2（CO）2的Fe（μ-η 2 :η 1 -CS 2）M（CO）5 ]。[Os 3（CO）12 ]的乙腈溶液与[Fe（CO）2的光解（PR 3）2（η 2 -CS 2）]导致[（PR 3）2（CO）2的Fe（μ-η 2 :η 1 -CS 2）锇3（CO）11 ]。的THF溶液的光解（PET 3）2（CO）2的Fe（μ-η 2 :η 1 -CS 2）M（CO）5 ]与宠物3个结果中形成的膦取代的配合物[（PPH 3）2（CO）2 Fe（µ-η 2∶η 1 -CS 2）M（CO）4（PEt 3）]。单晶X-射线衍射已被用来确定的分子结构[（PPH
• Reaction of the unsaturated mixed metal cluster [Os₃(µ-H)(CO)₁₀(µ-AuPR₃)](R = Ph, Et) with carbon monoxide and the chemistry of the products; the X-ray crystal structure of [Os₃(CO)₁₀(µ-AuPEt₃)₂]
  作者：Kevin Burgess、Brain F. G. Johnson、David A. Kaner、Jack Lewis、Paul R. Raithby、S. N. Azman、B. Syed-Mustaffa

  DOI：10.1039/c39830000455

  日期：——

  The cluster [Os3(CO)10(AuPR3)2](RPh, Et) may be prepared by the decarbonylation of [Os3(CO)11(AuPR3)2], or by the direct reaction of [Os3H(CO)11]– or [Os3(CO)11]2– with two equivalents of Au(PR3)Cl; an X-ray analysis of [Os3(CO)10(AuPR3)2] shows that both ‘AuPR3’ groups bridge the same short edge of the Os3 triangle.

  中文翻译：可以通过[Os3(CO)11(AuPR3)2]的去羰基化反应制备[Os3(CO)10(AuPR3)2](RPh, Et)，或者通过[Os3H(CO)11]–或[Os3(CO)11]2–与两当量Au(PR3)Cl的直接反应来制备；对[Os3(CO)10(AuPR3)2]进行的X射线分析显示，两个“AuPR3”基团都桥连在Os3三角形的同一条短边上。
• Some reactions of tetracarbonyldihydrido-osmium, octacarbonyldihydridodiosmium, and dodecacarbonyldihydridotriosmium
  作者：John R. Moss、William A. G. Graham

  DOI：10.1039/dt9770000089

  日期：——

  or Br). Heating [Os2X2(CO)8](X = Cl or Br) in n-heptane solution affords the hexacarbonyl compounds [Os2X2(CO)6]. The reactions of tin tetrachloride with [Os(CO)4}nH2](n= 1–3) are reported: for n= 1 or 2, the compounds [Os(CO)4}n H(SnCl3)](n= 1 or 2) have been isolated. The reaction of [Os2(CO)8H2] with triphenylphosphine yields the compounds [Os2(CO)7H2(PPh3)], [Os2(CO)6H2(PPh3)2], [Os(CO)4(PPh3)]

  [Os（CO）4 } n H 2 ]（n = 2或3）与四卤化碳的反应产生相应的二卤化物[Os（CO）4 } n X 2 ]（X = Cl或Br）。在正庚烷溶液中加热[Os 2 X 2（CO）8 ]（X = Cl或Br），得到六羰基化合物[Os 2 X 2（CO）6 ]。据报道四氯化锡与[Os（CO）4 } n H 2 ]（n = 1-3）的反应：对于n = 1或2，化合物[Os（CO）4 }已分离出n H（SnCl 3）]（n= 1或2）。[Os 2（CO） 8 H 2 ]与三苯基膦反应生成化合物[Os 2（CO） 7 H 2（PPh 3）]，[Os 2（CO） 6 H 2（PPh 3） 2 ]，[ Os（CO） 4（PPh 3）]和[Os（CO） 3 H 2（PPh 3）]。[Os 3（CO） 12 H 2 ]或[Os 2的热解（CO）8 H 2 ]给出氢化物[Os（CO）4
• Harvesting Highly Electronically Excited Energy to Triplet Manifolds: State-Dependent Intersystem Crossing Rate in Os(II) and Ag(I) Complexes
  作者：Cheng-Chih Hsu、Chao-Chen Lin、Pi-Tai Chou、Chin-Hung Lai、Chien-Wei Hsu、Chen-Huey Lin、Yun Chi

  DOI：10.1021/ja2107788

  日期：2012.5.9

  A series of newly synthesized Os(II) and Ag(I) complexes exhibit remarkable ratiometric changes of intensity for phosphorescence versus fluorescence that are excitation wavelength dependent. This phenomenon is in stark contrast to what is commonly observed in condensed phase photophysics. While the singlet to triplet intersystem crossing (ISC) for the titled complexes is anomalously slow, approaching

  一系列新合成的 Os(II) 和 Ag(I) 配合物表现出磷光强度与激发波长相关的荧光强度的显着比率变化。这种现象与凝聚相光物理学中通常观察到的现象形成鲜明对比。虽然标题复合物的单线态到三线态系统间交叉（ISC）异常缓慢，在最低电子激发态（S（1）→T（1））下接近数百皮秒，但更高的电子激发导致大大加速ISC (10(11)-10(12) s(-1))，与内部转换和/或振动弛豫竞争，如在重过渡金属配合物中常见的那样。该机制通过对标题配合物在 S(1) 状态中可忽略不计的金属 d 轨道贡献来合理化。反过来，高位激发态中显着的配体到金属电荷转移特性极大地增强了自旋轨道耦合，从而提高了 ISC 速率。最终结果是收获了朝向三重态的高电子激发能量，从而增强了磷光。
• On the mechanism of homogeneous catalytic hydrogenation using anion-promoted metal clusters
  作者：Janet L. Zuffa、Wayne L. Gladfelter

  DOI：10.1021/ja00275a079

  日期：1986.7

  alkene hydrogenation. While both spectroscopic and kinetic evidence supported a catalytic cycle involving an intact ruthenium triangle, no intermediates were isolated. With the hope of isolating such species, they turned to the osmium system and have found a rich chemistry that is reported here. The authors initially synthesized the anionic osmium isocyanato clusters using the same reaction found successful

  作者最近报告说，阴离子，尤其是异氰酸酯，可有效地将通常不活泼的 Ru/sub 3/(CO)/sub 12/ 转化为用于烯烃氢化的活性催化剂（在环境条件下为 5-6 周转/分钟）。虽然光谱和动力学证据都支持涉及完整钌三角形的催化循环，但没有分离出中间体。为了分离出这些物种，他们转向锇系统并发现了这里报道的丰富的化学物质。作者最初使用在钌化学中成功的相同反应合成了阴离子异氰酸锇簇。这里介绍的锇簇化学为所提出的中间体提供了证据。虽然不如钌系统活跃，

表征谱图