双(四甲基环戊二烯)铁 | 59568-28-4

• 物质功能分类: 化学试剂 - 有机试剂 - 烯烃（环状与无环状）
• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 中文名称: 双(四甲基环戊二烯)铁
• 英文名称: 1,1',2,2',3,3',4,4'-octamethylferrocene
• 英文别名: octamethylferrocene；Me₈Fc；Iron(2+);1,2,4,5-tetramethylcyclopenta-1,3-diene
• CAS: 59568-28-4
• 化学式: C₁₈H₂₆Fe
• 分子量: 298.251
• InChiKey: VSUTUDRPAASKEB-UHFFFAOYSA-N

物化性质

• 熔点：
  120-160 °C(lit.)
• 溶解度：
  可溶于氯仿（轻微）、乙酸乙酯（轻微）、甲醇（轻微、超声处理）
• 稳定性/保质期：
  避免接触氧化物

计算性质

• 辛醇/水分配系数(LogP)：
  5.28
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 安全说明：
  S22,S24/25

SDS

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Section 1: Product Identification
Chemical Name: Bis(tetramethylcyclopentadienyl)iron, min. 98%
CAS Registry Number: 59568-28-4
Formula: [(CH3)4C5H]2Fe
EINECS Number: none
Chemical Family: organometallic complexes
Synonym: None

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 59568-28-4 100% no data no data

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin, eyes and respiratory tract.
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: Ingestion may lead to vomiting, and diarrhea.
Acute Health Affects: Irritating to skin, eyes and respiratory tract.
Chronic Health Affects: No information available on long-term chronic effects.
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: none
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: carbon dioxide, foam or dry powder
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 If involved in a fire this material may emit irritating fumes.
Decomposion Products:
Unusual Fire or Explosion Hazards: No unusual fire or explosion hazards.

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SECTION 6: Accidental Release Measures
Spill and Leak Procedures: Small spills can be mixed with vermiculite or sodium carbonate and swept up.

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SECTION 7: Handling and Storage
Handling and Storage: Store in a cool, dry area away from heat and direct sunlight.

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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 protective clothing and gloves.
Ventilation: 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: 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 powder
Molecular Weight: 298.25
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: none
Solubility in Water: insoluble

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SECTION 10: Stability and Reactivity
Stability: air and moisture-stable material
Hazardous Polymerization: none
Conditions to Avoid: contact with strong oxidizing agents
Incompatibility: strong oxidizing agents
Decomposition Products: carbon dioxide, carbon monoxide, organic fumes, and iron oxide.

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SECTION 11: Toxicological Information
RTECS Data: No information available in RTECS.
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): Non-hazardous
Hazard Class (CFR): NA
Additional Hazard Class (CFR): NA
Packaging Group (CFR): NA
UN ID Number (CFR): NA
Shipping Name (IATA): Non-hazardous
Hazard Class (IATA): NA
Additional Hazard Class (IATA): NA
Packaging Group (IATA): NA
UN ID Number (IATA): NA

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SECTION 15: Regulatory Information
TSCA: not listed on the TSCA inventory
SARA (Title 313): Not reportable under SARA Title (313).
Second Ingredient: none

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  氯磺酸 、 双(四甲基环戊二烯)铁 以 乙酸酐 为溶剂， 反应 18.0h， 生成
  参考文献：
  名称：

  新型二茂铁基顺磁性阴离子八甲基二茂铁二磺酸盐及其TTF盐的结构和性质

  摘要：

  摘要 描述了以四苯基鏻 (PPh4) 盐形式获得的新型二茂铁基二磺酸根阴离子八甲基二茂铁二磺酸根 (Fe(C5(CH3)4(SO3))2) 的结构和性质。重结晶得到两种类型的盐，黄色晶体和绿色粉末。发现前一种成分是 (PPh4)2[Fe(C5(CH3)4(SO3))2]，其中 Fe(C5(CH3)4(SO3))2 是双离子的。绿色粉末被确定为 (PPh4)[Fe(C5(CH3)4(SO3))2]·0.4H2O，其中铁配合物是单阴离子的，尽管它有两个阴离子磺基。二茂铁部分的电荷为 + 1，温度相关的磁化率表明绿色盐是顺磁性的。PPh4 盐与 (TTF)3(BF4)2（TTF = 四硫富瓦烯）的复分解得到相同的化合物，(TTF)[Fe(C5(CH3)4(SO3))2]·3.5H2O，其中阴离子是顺磁性。这是第一种含有非抗磁性二茂铁基抗衡离子的 TTF 型盐。报道了 TTF 盐的结构和性质。

  DOI：

  10.1016/j.inoche.2015.08.018
• 作为产物：
  描述：

  1,2,3,4-四甲基-1,3-环戊二烯 、 iron(II) bromide 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以5.65 g的产率得到双(四甲基环戊二烯)铁
  参考文献：
  名称：

  1,1'-二乙酰基八甲基二茂铁：一个被忽视和逾期未交的合成子，导致八甲基二茂铁白垩烷的容易合成†

  摘要：

  本文描述了1,1'- diacetyloctamethylferrocene（的容易制备2）通过octamethylferrocene（酰化1）用乙酰氯。用POCl 3 / DMF为2的氯甲酰化可提供多种产物，包括高产率的1,1'-双-（1-氯乙烯基）八甲基二茂铁（3b）。化合物3b在氢氧化钠/ DMF水溶液中环化成带有1-二甲基氨基丁-1,3-二烯-柄的八甲基[1,4]-二茂铁fer烷（4）。

  DOI：

  10.1039/c6dt03820d
• 作为试剂：
  描述：

  4-氯-2,6-二硝基苯酚 在 盐酸 、 二氯化二硫 、 tin 、 双(四甲基环戊二烯)铁 、 tin(II) chloride dihdyrate 作用下， 以 乙腈 、 丙腈 为溶剂， 反应 4.0h， 生成
  参考文献：
  名称：

  Semiquinone-Bridged Bisdithiazolyl Radicals as Neutral Radical Conductors

  摘要：

  Semiquinone-bridged bisdithiazolyls 3 represent a new class of resonance-stabilized neutral radical for use in the design of single-component conductive materials. As such, they display electrochemical cell potentials lower than those of related pyridine-bridged bisdithiazolyls, a finding which heralds a reduced on-site Coulomb repulsion U. Crystallographic characterization of the chloro-substituted derivative 3a and its acetonitrile solvate 3a center dot MeCN, both of which crystallize in the polar orthorhombic space group Pna2(1), revealed the importance of intermolecular oxygen-to-sulfur (CO center dot center dot center dot SN) interactions in generating rigid, tightly packed radical pi-stacks, including the structural motif found for 3a center dot MeCN in which radicals in neighboring pi-stacks are locked into slipped-ribbon-like arrays. This architecture gives rise to strong intra- and interstack overlap and hence a large electronic bandwidth W. Variable-temperature conductivity measurements on 3a and 3a center dot MeCN indicated high values of sigma(300 K) (>10(-3) S cm(-1)) with correspondingly low thermal activation energies E-act, reaching 0.11 eV in the case of 3a center dot MeCN. Overall, the strong performance of these materials as f = 1/2 conductors is attributed to a combination of low U and large W. Variable-temperature magnetic susceptibility measurements were performed on both 3a and 3a center dot MeCN. The unsolvated material 3a orders as a spincanted antiferromagnet at 8 K, with a canting angle phi = 0.14 degrees and a coercive field H-c = 80 Oe at 2 K.

  DOI：

  10.1021/ja209841z

文献信息

• Tuning of Oxidation Potential of Ferrocene for Ratiometric Redox Labeling and Coding of Nucleotides and DNA
  作者：Anna Simonova、Ivan Magriñá、Veronika Sýkorová、Radek Pohl、Mayreli Ortiz、Luděk Havran、Miroslav Fojta、Ciara K. O'Sullivan、Michal Hocek

  DOI：10.1002/chem.201904700

  日期：2020.1.27

  7-deazaadenine and cytosine nucleosides and nucleoside triphosphates bearing either unsubstituted ferrocene, octamethylferrocene and ferrocenecarboxamide linked through an alkyne tether to position 7 or 5, respectively, were designed and synthesized. The modified dNFcX TPs were good substrates for KOD XL DNA polymerase in primer extension and were used for enzymatic synthesis of redox-labelled DNA probes. Square-wave

  设计并合成了三组分别带有未取代的二茂铁，八甲基二茂铁和二茂铁羧酰胺的7-脱氮腺嘌呤和胞嘧啶核苷和三磷酸核苷，它们通过炔烃系链连接至7或5位。修饰的dNFcX TPs是引物延伸中KOD XL DNA聚合酶的良好底物，可用于酶促合成氧化还原标记的DNA探针。方波伏安法显示，与二茂铁相比，八甲基二茂铁的氧化电势已移至较低值，而二茂铁羧酰胺的电势已移至较高电势。合成含有不同比例的Fc标记的A（dAFc）和FcPa标记的C（dCFcPa）的尾状PEX产物，并与固定在金电极上的捕获寡核苷酸杂交，以研究氧化还原标记的DNA的电化学。观察到了DNA中dAFc和dCFcPa碱基的清晰可辨，完全正交和比例峰，表明了它们可用于氧化还原编码核碱基以及直接电化学测量未知DNA序列中核碱基的相对比例。
• Stepwise Synthesis of Octamethylferrocene-1,1‘-dicarbaldehyde. Preparation of New Electron Donors for Charge-Transfer Complexes
  作者：Markus Hobi、Oliver Ruppert、Volker Gramlich、Antonio Togni

  DOI：10.1021/om9609978

  日期：1997.4.1

  preparation of various charge transfer complexes. The X-ray crystal structures of 1-[(1,3-benzodithiol-2-ylidene)methyl]-2,2‘,3,3‘,4,4‘,5,5‘-octamethylferrocene (11a), 1-[(1,3-dithiolo[4,5-b][1,3]dithiol-2-ylidene)methyl]-2,2‘,3,3‘,4,4‘,5,5‘-octamethylferrocene (11b), 1,1‘-bis[(1,3-benzodithiol-2-ylidene)methyl]-2,2‘,3,3‘,4,4‘,5,5‘-octamethylferrocene (12a), and 1,1‘-bis[(5,6-dihydro-1,3-dithiolo[4,5-b][1

  描述了从1,2,3,4-四甲基-5-（甲氧基羰基）环戊二烯（7）开始的八甲基二茂铁-1,1'-二甲醛（3）的逐步合成，涉及二茂铁的形成，酯还原为相应的二（羟甲基）衍生物9和MnO 2氧化。醛3容易在Wittig-Horner反应中与衍生自含硫杂环的不同膦酸酯反应，形成新的电子给体，可用于制备各种电荷转移络合物。1-[（（1,3-苯并二硫醇-2-亚甲基）甲基] -2,2'，3,3'，4,4'，5,5'-八甲基二茂铁（11a），1的X射线晶体结构-[（1,3-dithiolo [4,5- b] [1,3]二硫醇-2-亚甲基）-2,2'，3,3'，4,4'，5,5'-八甲基二茂铁（11b），1,1'-bis [（1， 3-苯并二硫醇-2-亚丙基）甲基] -2,2'，3,3'，4,4'，5,5'-八甲基二茂铁（12a）和1,1'-双[（5,6-二氢-1,3-二硫代[4,5- b ] [1,4]二硫代-2-亚基）甲基]
• Tuning the Geometric and Electronic Structure of Synthetic High-Valent Heme Iron(IV)-Oxo Models in the Presence of a Lewis Acid and Various Axial Ligands
  作者：Melanie A. Ehudin、Leland B. Gee、Sinan Sabuncu、Augustin Braun、Pierre Moënne-Loccoz、Britt Hedman、Keith O. Hodgson、Edward I. Solomon、Kenneth D. Karlin

  DOI：10.1021/jacs.9b00795

  日期：2019.4.10

  of the protic Lewis acid, 2,6-lutidinium triflate (LutH+), with (or without) DCHIm. Mössbauer, rR, and XAS spectroscopic data indicated the formation of molecular Lewis acid ferryl adducts (rather than full protonation). The reduction potentials of these novel Lewis acid adducts were bracketed through addition of outer-sphere reductants. The oxidizing capabilities of the ferryl species with or without

  在所涉及的含血红素酶（P-450s、过氧化物酶、过氧化氢酶和细胞色素 c 氧化酶）的催化循环中，观察到或提出了高价弗瑞尔物种（例如 (Por)FeIV=O、Cmpd-II）的关键氧化中间体在生物呼吸和氧化代谢中。在此，制备了各种轴向连接的铁 (IV)-氧代复合物以检查碱基身份的影响。这些是通过添加各种轴向配体（1,5-二环己基咪唑 (DCHIm)、系留咪唑系统和 3,5-二甲氧基苯酚盐和咪唑盐的钠衍生物）产生的。通过紫外-可见光、电子顺磁共振 (EPR)、57Fe Mössbauer、Fe X 射线吸收 (XAS)、和 54/57Fe 共振拉曼 (rR) 光谱以确认它们的形成并比较这些血红素铁 (IV)-氧代物种的电子和几何结构上的轴向配体扰动。穆斯堡尔研究证实，轴向连接的衍生物是铁 (IV) 和六配位配合物。XAS 和 54/57Fe rR 数据与铁氧键的轻微伸长相关，随着轴向配体的捐赠增加。第一个报道的合成
• Charge-transfer complexes from decamethylferrocene and 1,4-quinone derivatives: neutral–ionic phase diagrams for metallocene complexes
  作者：Tomoyuki Mochida、Yusuke Funasako、Hiroko Azumi

  DOI：10.1039/c1dt10200a

  日期：——

  Charge-transfer (CT) complexes of ferrocenes with 1,4-quinone derivatives were investigated. Deca- and octamethylferrocene complexes with 1,4-naphthoquinone derivatives were prepared and structurally characterized; these were neutral 1 : 2 DA complexes with mixed-stack structures. The formation of complexes with 1,4-benzoquinones was examined by applying solvent-drop grinding. CT energies and phase transitions in these neutral and other ionic complexes were investigated. Their electronic states are discussed on the basis of the phase diagrams derived for mixed-stack ferrocene-based CT complexes, taking into account their dependence on the DA ratio, dimensionality, and intermolecular interactions.

  研究了与1,4-苯醌衍生物的铁氟烯（ferrocene）电荷转移（CT）复合物。制备并对十甲基和八甲基铁氟烯与1,4-萘醌衍生物的复合物进行了结构表征；这些复合物是中性的1:2供体-受体（DA）复合物，具有混合堆叠结构。通过施加溶剂滴磨法研究与1,4-苯醌的复合物形成。考察了这些中性和其他离子复合物的电荷转移能量及相变。基于为混合堆叠铁氟烯基电荷转移复合物得出的相图，讨论了它们的电子状态，并考虑了它们对DA比例、维度和分子间相互作用的依赖性。
• Crystal Structures and Phase Sequences of Metallocenium Salts with Fluorinated Anions: Effects of Molecular Size and Symmetry on Phase Transitions to Ionic Plastic Crystals
  作者：Tomoyuki Mochida、Yusuke Funasako、Mai Ishida、Shingo Saruta、Takashi Kosone、Takafumi Kitazawa

  DOI：10.1002/chem.201603170

  日期：2016.10.24

  The Tf2N salts commonly undergo phase transitions from an ordered phase at low temperatures to an anion‐disordered phase, followed by a plastic phase and finally melt at high temperatures. All these salts exhibit a phase transition to a plastic phase, and the transition temperature generally decreases with decreasing cation size and increasing anion size. The crystal structures of these salts comprise

  夹心化合物通常表现出各种相变，包括到塑性相的相变。为了阐明金属茂盐中相变的一般特征，[Fe（C 5 Me 5）2 ] X（[ 1 ] X），[Co（C 5 Me 5）2 ] X（已经研究了[ 2 ] X）和[Fe（C 5 Me 4 H）2 ] X（[ 3 ] X），其中抗衡阴离子（X）为Tf 2 N（=（CF 3 SO 2）2 N −），OTf（= CF 3SO 3 -），PF 6和BF 4。Tf 2 N盐通常会经历从低温有序相到阴离子无序相的相变，然后是塑性相，最后在高温下熔融。所有这些盐都表现出向塑性相的相转变，并且转变温度通常随着阳离子尺寸的减小和阴离子尺寸的增加而降低。这些盐的晶体结构包含阳离子和阴离子的交替排列。这些盐中约有一半在低温下表现出相变，这主要与阴离子的有序无序有关。