三羰基(η-环戊二烯基)合锰 | 12079-65-1

• 物质功能分类: 有机原料 - 有机金属类化合物 - 有机锰
• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 三羰基(η-环戊二烯基)合锰
• 中文别名: 三羰基环戊二烯锰；环戊二烯三羰基锰(CMT)；三羰基环戊二烯合锰；三羰基环戊二烯锰(I)；三羰基环戊二烯基锰；CMT；环戊二烯三羰基锰
• 英文名称: cymantrene
• 英文别名: tricarbonyl(η⁵-cyclopentadienyl)manganese；(η5-cyclopentadienyl) tricarbonyl manganese (I)；(μ(5)-cyclopentadienyl)(tricarbonyl)manganese；(η5-cyclopentadienyl)tricarbonylmanganese(I)；tricarbonyl(η5-cyclopentadienyl)manganese(I)；(η(5)-cyclopentadienyl)tricarbonylmanganese
• CAS: 12079-65-1
• 化学式: C₈H₅MnO₃
• 分子量: 204.064
• InChiKey: OWUDJNGZBGIAFN-UHFFFAOYSA-N

物化性质

• 熔点：
  72-76 °C(lit.)
• 暴露限值：
  ACGIH: TWA 0.1 mg/m3 (Skin)OSHA: Ceiling 5 mg/m3NIOSH: IDLH 500 mg/m3; TWA 0.1 mg/m3; TWA 1 mg/m3; STEL 3 mg/m3
• 稳定性/保质期：
  常温常压下稳定，应避免与氧化物接触。

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

安全信息

• 职业暴露等级：
  D
• 职业暴露限值：
  TWA: 0.1 mg/m3 [skin]
• TSCA：
  Yes
• 危险等级：
  6.1
• 危险品标志：
  T+
• 安全说明：
  S28,S36/37,S45
• 危险类别码：
  R28
• WGK Germany：
  3
• 海关编码：
  29310099
• 危险品运输编号：
  UN 2811 6.1/PG 2
• RTECS号：
  OO9720000
• 包装等级：
  II
• 危险类别：
  6.1
• 危险性防范说明：
  P264,P270,P301+P310+P330,P405,P501
• 危险性描述：
  H300
• 储存条件：
  常温下应密闭避光保存，并存放在通风且干燥的地方。

SDS

Name:	Cyclopentadienylmanganese Tricarbonyl Material Safety Data Sheet
Synonym:	Cymantren
CAS:	12079-65-1

Section 1 - Chemical Product MSDS Name:Cyclopentadienylmanganese Tricarbonyl Material Safety Data Sheet
Synonym:Cymantren

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
12079-65-1	Cyclopentadienylmanganese Tricarbonyl	ca 100	235-142-4

Hazard Symbols: T+
Risk Phrases: 26/27/28

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Very toxic by inhalation, in contact with skin and if swallowed.Air sensitive.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation.
Ingestion:
May be fatal if swallowed. May cause irritation of the digestive tract. May cause central nervous system depression.
Inhalation:
May cause respiratory tract irritation. May cause lung damage.
Chronic:
May cause lung damage.

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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:
Never give anything by mouth to an unconscious person. Get medical aid. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water. 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. Do NOT use mouth-to-mouth resuscitation.
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. Place under an inert atmosphere.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Use with adequate ventilation. Avoid contact with eyes, skin, and clothing. Do not breathe dust, vapor, mist, or gas. Keep container tightly closed. Avoid ingestion and inhalation. Handle under an inert atmosphere. Store protected from air. Use only in a chemical fume hood.
Storage:
Store in a cool, dry, well-ventilated area away from incompatible substances. Do not expose to air. Store under an inert atmosphere.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 12079-65-1: United States OSHA: 5 mg/m3 Ceiling (as Mn) (listed under Mangan compounds, n.o.s.).
Belgium - TWA: 0.1 mg/m3 VLE (as Mn) France - VME: 0.1 mg/m3 VME (as Mn) Germany: 0.1 mg/m3 TWA Germany: Skin absorber Japan: (listed as manganese compounds, n.o.s.): 0.3 mg/m3 OEL (ex organic compounds, as Mn) Malaysia: 0.1 mg/m3 TWA (as Mn) Netherlands: 0.3 mg/m3 STEL (as Mn) Netherlands: 0.1 mg/m3 MAC (as Mn) Russia: 0.1 mg/m3 TWA (as Mn) Spain: 0.1 mg/m3 VLA-ED (as Mn) 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:
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: yellow
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 72 - 76 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: insoluble
Specific Gravity/Density:
Molecular Formula: C8H5MnO3
Molecular Weight: 203.9712

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable at normal temperatures in tightly closed containers under an inert atmosphere.
Conditions to Avoid:
Incompatible materials, dust generation, exposure to air, 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# 12079-65-1: OO9720000 LD50/LC50:
CAS# 12079-65-1: Oral, mouse: LD50 = 150 mg/kg; Oral, rat: LD50 = 22 mg/kg.
Carcinogenicity:
Cyclopentadienylmanganese Tricarbonyl - Not listed by ACGIH, IARC, or NTP.
Other:
See actual entry in RTECS for complete information.

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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: II
IMO
Shipping Name: METAL CARBONYLS, N.O.S.
Hazard Class: 6.1
UN Number: 3281
Packing Group: II
RID/ADR
Shipping Name: METAL CARBONYLS, N.O.S.
Hazard Class: 6.1
UN Number: 3281
Packing group: II

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: T+
Risk Phrases:
R 26/27/28 Very toxic by inhalation, in contact with
skin and if swallowed.
Safety Phrases:
S 28A After contact with skin, wash immediately with
plenty of water.
S 36/37/39 Wear suitable protective clothing, gloves
and eye/face protection.
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# 12079-65-1: No information available.
Canada
CAS# 12079-65-1 is listed on Canada's NDSL List.
CAS# 12079-65-1 is listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 12079-65-1 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

类别：有毒物质
毒性分级：剧毒
急性毒性：

• 大鼠 LD50：22毫克/公斤
• 小鼠 LD50：150毫克/公斤

可燃性危险特性：可燃；火场分解产生有毒的氧化锰烟雾

储运特性：

• 库房应保持低温、通风和干燥
• 防火措施需落实
• 与氧化剂及食品原料分开存放

灭火剂：

• 水
• 二氧化碳
• 干粉
• 砂土

职业标准：

• 时间加权平均容许浓度（TWA）：0.1毫克/立方米
• 短时间接触容许浓度（STEL）：0.3毫克/立方米

反应信息

• 作为反应物：
  描述：

  三羰基(η-环戊二烯基)合锰 生成 锰
  参考文献：
  名称：

  Segal, L. D.; Krichevskaya, O. D.; Belozerskii, N. A., Zhurnal Neorganicheskoi Khimii, 1967, vol. 12, p. 592 - 593

  摘要：

  DOI：
• 作为产物：
  描述：

  (η5-cyclopentadienyl)dicarbonylmanganese 在 一氧化碳 作用下， 以 gaseous matrix 为溶剂， 生成 三羰基(η-环戊二烯基)合锰
  参考文献：
  名称：

  气相配位不饱和光片段（η5-C5H5）Mn（CO）x（x = 2和1）的时间分辨红外研究

  摘要：

  Time-resolved infrared spectroscopy is used to study the coordinatively unsaturated species eta-5-C5H5)Mn(CO)x (x = 2 and 1) generated by 266- and 355-nm laser photolysis of (eta-5-C5H5)Mn(CO)3 in the gas phase. (eta-5-C5H5)Mn(CO) is the predominant photoproduct upon 266-nm photolysis while both (eta-5-C5H5)Mn(CO) and (eta-5-C3H5)Mn(CO)2 am produced upon 355-nm photolysis. IR spectra in the region of 1820-2033 cm-1 are assigned for the coordinatively unsaturated species (eta-5-C5H5)Mn(CO)x and found to be in major disagreement with those obtained in condensed phases. The rate constants for the reactions of (eta-5-C5H5)Mn(CO)2 and (eta-5-C5H5)Mn(CO) with CO are determined to be (5.9 +/- 0.4) x 10(11) and (6.7 +/- 0.2) x 10(12) cm3 mol-1 s-1, respectively. The rate constant for the reaction of (eta-5-C5H5)Mn(CO) with CO is on the order of 1/10 gas kinetic while the corresponding value for (eta-5-C5H5)Mn(CO)2 is over an order of magnitude smaller. The magnitudes of the rate constants for the reactions of (eta-5-C5H5)Mn(CO)x with CO are compared with those of (eta-6-C6H6)Cr(CO)x previously observed and are discussed in terms of the change of spin states of these reactions. In addition, it is found that the presence of care gas Q (Q = Ar, He, and Xe) has remarkable influence on the kinetic behavior of (eta-5-C5H5)Mn(CO)2, implying the formation of rare-gas complexes (eta-5-C5H5)Mn(CO)2.Q in the gas phase.

  DOI：

  10.1021/j100198a031
• 作为试剂：
  描述：

  1,3-环庚二烯 、 3-tert-butyl-1,1,2,2-tetrafluoro-1,2-disilacyclobutene 在 三羰基(η-环戊二烯基)合锰 作用下， 生成 、 、 4-tert-Butyl-1,1,3,3-tetrafluoro-2-(2-methylene-cyclopentyl)-2,3-dihydro-1H-[1,3]disilole
  参考文献：
  名称：

  Chiang, Hui-Jean; Liu, Chao-Shiuan, Journal of Organometallic Chemistry, 1992, vol. 438, # 1.2, p. C9 - C12

  摘要：

  DOI：

文献信息

• Radikalkomplexe vom typ Cp(CO)2MnXR. (X = S, Se)
  作者：Andreas Winter、Gottfried Huttner、Margarete-Gottlieb、Ibrahim Jibril

  DOI：10.1016/0022-328x(85)80048-6

  日期：1985.5

  CpMn(CO)2ER (E = S, Se) compounds [1] belong to the rare radical derivatives of the CpMn(CO)2 fragment. We describe herein the syntheses, electrochemistry, and organometallic reactions of Cp★Mn(CO)2SR 1 (1a: R = t-C4H9, 1b: R = 2-adamantyl) and CpM(CO)2SePh (2).

  CpMn（CO）2 ER（E = S，Se）化合物[1]属于CpMn（CO）2片段的稀有自由基衍生物。我们在本文中描述的合成，电化学，和Cp的有机金属反应★的Mn（CO）2 SR 1（1A：R =的tC 4 ħ 9，1B：R = 2-金刚烷基）和CPM（CO）2 SEPH（2）。
• Cyclopentadienyl transfer reaction: thermal reaction between Re2(CO)10 and a series of cyclopentadienyl transition metal complexes
  作者：Siden Top、Christophe Lescop、Jean-Sébastien Lehn、Gérard Jaouen

  DOI：10.1016/s0022-328x(99)00618-x

  日期：2000.1

  by the fact that the hapticity of the ligand in the Ti and Ni substrates changes easily allowing for an extra temporary coordination of [Re2(CO)9], for example, generated in situ and leading to CpRe(CO)3. Heating titanium compound 1 with Re2(CO)10 led to CpRe(CO)3 and the substituted cyclopentadienyltricarbonylrhenium compound 2 with yields of 36 and 37%, respectively.

  描述了一系列有机金属环戊二烯基配合物与作为Re（CO）3来源的Re 2（CO）10之间的热配体转移反应。获得了预期的CpRe（CO）3络合物，这是一种非常坚固的分子，其收率范围很差，例如当环戊二烯前体热稳定性太高或易分解时，太容易产生挥发性环戊二烯分子，从而达到优异的收率。与Cp 2 TiCl 2或Cp 2 Ni一样。我们通过以下事实来解释观察到的行为，即Ti和Ni基体中配体的触觉容易改变，从而允许[Re 2（CO）的额外临时配位。例如，图9 ]是原位产生并导致CpRe（CO）3。将钛化合物1与Re 2（CO）10加热，分别得到CpRe（CO）3和取代的环戊二烯基三羰基hen化合物2，产率分别为36％和37％。
• Synthesis, Characterization, and Structural Studies of Multimetallic Ferrocenyl Carbene Complexes of Group VII Transition Metals
  作者：Daniela I. Bezuidenhout、Simon Lotz、Marilé Landman、David C. Liles

  DOI：10.1021/ic101784w

  日期：2011.2.21

  followed by the Fischer method of carbene preparation, resulted in formation of the novel biscarbene complexes with bridging ferrocen-1,1′-diyl (Fc′) substituents [π-Fe(C5H4)2-C,C′}C(OEt)MLx}2] (1b, MLx = MnCp(CO)2; 3b, MLx = Re2(CO)9) or the unusual bimetallacyclic bridged biscarbene complexes [π-TiCp2O2−O,O′}π-Fe(C5H4)2-C,C′}CMLx}2] (2b, MLx = MnCp(CO)2; 4b, MLx = Re2(CO)9). The target compounds

  合成了含有至少两个或三个不同的过渡金属取代基的VII族过渡金属（Mn和Re）的费歇尔卡宾配合物，它们都与卡宾碳原子电子接触。对卡宾多金属化合物中的结构特征及其与键的相关性进行了研究，因为它们代表了多金属卡宾组件中可能存在的反应位点。对于[ML x C（OR）R'}]类型的配合物（ML x = MnCp（CO）2或Re 2（CO）9），选择二茂铁基（Fc）作为R'取代基，而或在乙氧基或钛氧基之间系统地改变取代基，以生成配合物1a（ML x= MnCp（CO）2，R = Et，R'= Fc），2a（ML x = MnCp（CO）2，R = TiCp 2 Cl，R'= Fc），3a（ML x = Re 2（CO）在图9中，R ＝ Et，R′＝ Fc）和4a（ML x＝ Re 2（CO）9，R ＝ TiCp 2 Cl，R′＝ Fc）。在高温下用n -BuLi / TMEDA直接对二茂铁进行锂化，
• Hydrosilylation of Aldehydes and Ketones Catalyzed by Half-Sandwich Manganese(I) N-Heterocyclic Carbene Complexes
  作者：Jianxia Zheng、Saravanakumar Elangovan、Dmitry A. Valyaev、Rémy Brousses、Vincent César、Jean-Baptiste Sortais、Christophe Darcel、Noël Lugan、Guy Lavigne

  DOI：10.1002/adsc.201300905

  日期：2014.3.24

  Easily available manganese(I) N‐heterocyclic carbene (NHC) complexes, Cp(CO)2Mn(NHC), obtained in one step from industrially produced cymantrene, were evaluated as pre‐catalysts in the hydrosilylation of carbonyl compounds under UV irradiation. Complexes with NHC ligands incorporating at least one mesityl group led to the most active and selective catalytic systems. A variety of aldehydes (13 examples)

  容易获得的锰（I）N-杂环卡宾（NHC）络合物，从工业生产的cymantrene一步获得的Cp（CO）2 Mn（NHC）被评估为在UV辐射下羰基化合物氢化硅烷化反应中的预催化剂。具有NHC配体的配合物至少结合了一个1，3，3，5-三甲磺酰基，形成了最活跃和选择性最高的催化体系。在温和的条件下[Cp（CO）2 Mn（IMes）（1 mol％），Ph 2 SiH 2（1.5当量），hν（350 nm ）有效地还原了各种醛（13个实例）和酮（11个实例）），甲苯，25°C，1–24小时]，具有良好的官能团耐受性。
• Organometallic Isocyanocyclopentadienides:  A Combined Synthetic, Spectroscopic, Structural, Electrochemical, and Theoretical Investigation
  作者：Thomas C. Holovics、Stephan F. Deplazes、Masaharu Toriyama、Douglas R. Powell、Gerald H. Lushington、Mikhail V. Barybin

  DOI：10.1021/om049842n

  日期：2004.6.1

  compounds [Cr(CNR)6]0,1+,2+ (R = Fc, Cm) are remarkable due to the incorporation of seven transition metal atoms within relatively compact ML6 motifs. The physical, chemical, electrochemical, and spectroscopic properties of the structurally characterized series [Cr(CNFc)6]0,1+,2+ indicate that the electronic influence of the ferrocenyl moiety, often compared to an alkyl group, is in fact more similar

  本文报道了两种有机金属异氰基环戊二烯化物的化学反应，它们代表了新兴的一类新的并入非苯环π系统的芳族异氰化物。氨基二茂铁与甲酸苯酯/苯酚的混合物相互作用，然后将所得二茂铁基甲酰胺与POCl 3脱水，可高产率地产生空气和热稳定的异氰基二茂铁（CNFc，Fc =二茂铁）。治疗lithiocymantrene，LiCm（CM =（η 5 -C 5 H ^ 4）的Mn（CO）3），用甲苯磺酰叠氮化物，得到热敏cymantrenyl叠氮化物。未经隔离，CmN 3被NaBH 4还原形成氨基环丁烯，将其转变为对空气稳定但对热和光敏感的异氰基环戊二烯，CNCm。结合6当量的CNR（R = Fc，Cm）与双（萘）铬（0），得到Cr（CNR）6。Cr（CNR）6与Ag +的连续单电子氧化产生了相应的顺磁性[Cr（CNR）6 ] +和[Cr（CNR）6 ] 2+。化合物[Cr（CNR）6 ] 0,1 +，2 +（R