decabromoferrocene | 65929-09-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: decabromoferrocene
• 英文别名: iron(2+);1,2,3,4,5-pentabromocyclopenta-1,3-diene
• CAS: 65929-09-1
• 化学式: C₁₀Br₁₀Fe
• 分子量: 974.997
• InChiKey: HMWKYHMHIZNSHV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.43
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二甲基一氯硅烷 、 decabromoferrocene 在 magnesium 、 1,2-二溴乙烷 作用下， 以 四氢呋喃 为溶剂， 生成 (1,2,3,4-tetra(dimethylsilyl)cyclopentadienyl)(1,2,3-tri(dimethylsilyl)cyclopentadienyl)iron(II)
  参考文献：
  名称：

  二茂铁的 Persilylation：空间拥挤的金属配合物的终极纪律

  摘要：

  我们报告了第一个通过十溴二茂铁金属化制备和结构表征的全硅烷基化茂金属。尽管由于甲硅烷基的空间和电子效应导致金属化中间体的亲核性降低，格氏条件被证明是不充分的，但逐步的锂-卤素交换产生了多甲硅烷基化合物的复杂混合物 FeC 10 DMS n H 10− n ( n= 10, 9, 8) 包括目标 decasylated 二茂铁。这些混合物被成功分离，允许通过 DFT 计算支持的 XRD、CV、NMR 和 UV/vis 光谱系统研究硅烷化对二茂铁的影响。该发现用于开发一种高产率且简单的制备方法，以生成十倍取代的过度拥挤的二茂铁 FeC 10 DMS 8 Me 2。

  DOI：

  10.1039/d3dt01133j
• 作为产物：
  描述：

  decakis(acetoxymercurio)ferrocene 、 potassium tribromide 以 水 为溶剂， 以60%的产率得到decabromoferrocene
  参考文献：
  名称：

  Permercuration of Ferrocenes and Ruthenocenes. New Approaches to Complexes Bearing Perhalogenated Cyclopentadienyl Ligands

  摘要：

  Treatment of ferrocene with mercuric trifluoroacetate (10 equiv) and mercuric oxide (5 equiv) in 1:1 diethyl ether/ethanol afforded decakis[(trifluoroacetoxy)mercurio]ferrocene (60%) as a yellow-orange powder. Reaction with cupric chloride dihydrate in acetone yielded mixtures of partially chlorinated ferrocenes, of which decachloroferrocene was a minor component. Treatment of ferrocene with mercuric acetate (10 equiv) in refluxing dichloroethane for 18 h afforded decakis(acetoxymercurio)ferrocene (95%). Halogenation of decakis(acetoxymercurio)ferrocene with cupric chloride dihydrate in acetone, potassium tribromide in water, or potassium triiodide in water afforded decachloroferrocene (27%), decabromoferrocene (60%), and decaiodoferrocene (67%), respectively. Examination of the H-1 NMR spectra of crude decachloroferrocene and decabromoferrocene revealed small amounts (less-than-or-equal-to 5%) of partially halogenated ferrocenes, which suggested that decakis(acetoxymercurio)ferrocene was not completely decamercurated. Treatment of ruthenocene with mercuric acetate (10 equiv) in refluxing dichloroethane afforded decakis(acetoxymercurio)ruthenocene (88%). Reaction of decakis(acetoxymercurio)ruthenocene with cupric chloride dihydrate in acetone, potassium tribromide in water, or potassium triiodide in water afforded decachlororuthenocene (73%), decabromoruthenocene (47%), and decaiodoruthenocene (39%), respectively. Inspection of the H-1 NMR spectra of crude decachlororuthenocene and decabromoruthenocene showed no resonances that could be attributed to partially halogenated ruthenocenes, which indicates that decakis(acetoxymercurio)ruthenocene was greater-than-or-equal-to 98% decamercurated. Treatment of pentamethylruthenocene with mercuric acetate in 1:1 diethyl ether/ethanol afforded pentakis(acetoxymercurio)pentamethylruthenocene (88%). Pentakis(acetoxymercurio)pentamethylruthenocene showed hindered rotation of the mercury-acetate groups in the H-1 NMR spectra. Halogenation afforded pentachloropentamethylruthenocene (67%), pentabromopentamethylruthenocene (35%), and pentaiodopentamethylruthenocene (60%). Treatment of (eta5-pentamethylcyclopentadienyl)(eta5-indenyl)ruthenium(II) with mercuric acetate (greater-than-or-equal-to 3 equiv) in 1:1 diethyl ether-ethanol afforded (eta5-1,2,3-tris(acetoxYmercurio)indenyl)(eta5-pentamethylcyclopentadienyl)ruthenium(II) (99%), which could be brominated and iodinated to afford (eta5-1,2,3-tribromoindenyl)(eta5-pentamethylcyclopentadienyl) ruthenium(II) (29%) and (eta5-1,2,3-triiodoindenyl)(eta5-pentamethylcyclopentadienyl)r uthenium(II) (66%). The structure of (eta5-1,2,3-triiodoindenyl)(eta5-pentamethylcyclopentadienyl)r uthenium(II) was determined, showing that it crystallized in the monoclinic space group P2(1)/c with cell dimensions a 15.934(3) angstrom, b = 10.308(4) angstrom, c = 12.530 (5) angstrom, beta = 93.53(2)-degrees, V = 2054(1) angstrom3, and Z = 4.

  DOI：

  10.1021/om00020a017

文献信息

• Preparation and One-Electron Oxidation of Decabromoferrocene
  作者：Susanne M. Rupf、Irina S. Dimitrova、Gabriel Schröder、Moritz Malischewski

  DOI：10.1021/acs.organomet.2c00157

  日期：2022.5.23

  We report an improved synthesis as well as a spectroscopical, structural, and electrochemical characterization of decabromoferrocene (FeC10Br10) and relevant side products. One-electron oxidation of decabromoferrocene (E1/2 = 1.095 V vs FeCp20/+) was achieved by AsF5 in liquid SO2. The crystal structure of decabromoferrocenium hexafluoroarsenate, [FeC10Br10][AsF6], represents the first example of an

  我们报告了十溴二茂铁 (FeC 10 Br 10 ) 和相关副产物的改进合成以及光谱、结构和电化学表征。十溴二茂铁的单电子氧化（E 1/2 = 1.095 V vs FeCp 2 0/+）通过AsF 5在液体SO 2中实现。十溴二茂铁六氟砷酸盐的晶体结构，[FeC 10 Br 10 ][AsF 6 ]，代表了第一个分离的和结构表征的全卤化二茂铁盐的例子。
• Mercury(II) Trichloroacetate. Part II. Formation and Use as a Versatile Reagent in Ferrocene Chemistry
  作者：Alberto Federman Neto、Aurea Donizete Lanchote Borges、Ivan Pérsio de Arruda Campos、Joseph Miller

  DOI：10.1080/00945719708003158

  日期：1997.11

  The preparation of a methanolic solution of mercury(II) trichloroacetate is described. This reagent is used in an improved decamercuration of ferrocene. Decamercurated ferrocene is converted to decahaloferrocenes and used as the starting material in a new method for the synthesis of decadeuteroferrocene.