1,1',3,3'-tetra-t-butylferrocene | 1317-17-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,1',3,3'-tetra-t-butylferrocene
• 英文别名: 1,1',3,3'-tetra-tert-butylferrocene；1,1',3,3'-tetra(2-methyl-2-propyl)ferrocene；2,2',4,4'-tetra-tert-butylferrocene；1,3-Ditert-butylcyclopenta-1,3-diene;iron(2+)；1,3-ditert-butylcyclopenta-1,3-diene;iron(2+)
• CAS: 1317-17-5
• 化学式: C₂₆H₄₂Fe
• 分子量: 410.466
• InChiKey: GDNSZQMZEWNQFG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.0
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  5-羰基-L-脯氨酰-L-苯基丙氨酰-L-酪氨酰甘氨酰-L-亮氨酰-L-蛋氨酸酰胺 、 1,1',3,3'-tetra-t-butylferrocene 以 二氯甲烷 、 乙腈 为溶剂， 反应 6.0h， 生成 C₂₆H₄₂Fe⁽¹⁺⁾*O₄Re^(1-)
  参考文献：
  名称：

  1,1'，2,2'-和1,1'，3,3'-四叔丁基二茂铁（1+）阳离子的X射线结构和电子性质

  摘要：

  摘要用AgReO4在二氯甲烷中氧化化合物1,1'，2,2'-和1,1'，3,3'-四叔丁基二茂铁（分别为1,2-BUT和1,3-BUT）从丙酮中重结晶后，分离出二茂铁盐（1+），为[1,2-BUT +] [ReO4-]和[1,3-BUT +] [ReO4-]·的深蓝色或深绿色晶体。丙酮，分别适用于X射线衍射。如从中性二茂铁的已知结构所预期的，二叔丁基环戊二烯基（Cp'）环在1,2-BUT +阳离子中实际上是平行的，并且在1,3-BUT +阳离子中倾斜了11.6°。与相应的中性二茂铁相比，两个阳离子中的Fe C距离跨度更大，平均而言更长。UV-Vis光谱显示，黄色的1,2-BUT（442 nm）的λmax低于橙色的1,3-BUT（466 nm），蓝色的1，2-BUT +（674 nm）低于绿色1,3-BUT +（682 nm）。此外，此处首次报道的在二氯甲烷中通过循环伏安法测定的E1 / 2（+

  DOI：

  10.1016/j.poly.2016.09.027
• 作为产物：
  描述：

  二茂铁 、 氯代叔丁烷 在 三氟化硼乙醚 作用下， 以 正己烷 为溶剂， 以23%的产率得到1,1',3,3'-tetra-t-butylferrocene
  参考文献：
  名称：

  1,1',4,4'-四叔丁基铀二茂和 1,1',3,3'-四叔丁基二茂铁中环旋转的障碍

  摘要：

  1,1',4,4'~四叔丁基铀二茂的{sup 1}H-NMR谱显示叔丁基质子的单峰和环质子的三个单峰。聚结发生在 -65 至 -85°C，每个峰在较低温度下分裂，对应于 8.3 Kcal mol{sup -1} 的 {Delta}G{sup {ne}} 旋转{sup -1} 也观察到聚结 1,1获得',3,3'-四叔丁基二茂铁和相应的{Delta}G{sup {ne}} = 13.1 Kcal mol{sup 1}。

  DOI：

  10.1021/ja00402a001

文献信息

• Teaching Ferrocenium How to Relax: A Systematic Study on Spin–Lattice Relaxation Processes in <i>tert</i> ‐Butyl‐Substituted Ferrocenium Derivatives
  作者：Matthias Reiners、Dirk Baabe、Peter Schweyen、Matthias Freytag、Peter G. Jones、Marc D. Walter

  DOI：10.1002/ejic.201600873

  日期：2017.1.10

  temperature-dependent line shapes attributed to unusually slow paramagnetic relaxation on the 57Fe Mossbauer time scale. The pertinent spin–spin and spin–lattice (Orbach and Raman) relaxation parameters were determined for these materials and further substantiate the trends observed by our EPR spectroscopic and solid-state magnetic susceptibility studies.

  制备了具有四个、五个或六个叔丁基取代基和多种抗衡阴离子（[BF4]–、[SbF6]– 和 [PF6]–）的空间位阻二茂铁盐。这些材料的电子结构通过各种物理技术进行了研究，包括电子顺磁共振 (EPR) 和穆斯堡尔光谱以及固态磁化率测量。自旋轨道耦合和低对称性畸变将这些化合物中的电子基态 (2E2g) 分裂为两个克莱默双重态 (Ψa 和 Ψb)；这些状态之间的能量差异通过 EPR 光谱和磁化率测量进行评估，并且随着二茂铁部分的空间需求增加而降低。通过固态磁化率测量获得了关于第一激发态 (2A1g) 的更多信息，这也表明增加的空间体积导致 2E2g(Ψa) 和 2A1g 状态之间的能隙减小。Mossbauer 光谱揭示了与温度相关的线形状，这归因于 57Fe Mossbauer 时间尺度上异常缓慢的顺磁弛豫。确定了这些材料的相关自旋-自旋和自旋-晶格（奥尔巴赫和拉曼）弛豫参数，并进一步证实了我们的
• The coordination chemistry of 2,4-di( tert -butyl)pentadienyl revisited
  作者：Matthias Reiners、Dirk Baabe、Peter Schweyen、Matthias Freytag、Peter G. Jones、Marc D. Walter

  DOI：10.1016/j.ica.2014.06.020

  日期：2014.10

  The coordination chemistry of the previously neglected 2,4-di(tert-butyl)pentadienyl (Pdl') ligand with transition metals is explored. Several open metallocenes [(eta(5)-Pdl')(2)M] (M = Ti (3), V (4) and Cr (5)) were prepared and characterized by various spectroscopic techniques and X-ray diffraction. Attempts to prepare the open ferrocene [(eta(5)-Pdl')(2)Fe] were hampered by its high thermal instability, which leads to the formation of iron metal and 2,4,7,9-tetra-tert-butyl-1,3,7,9-decatetraene (2). Nevertheless, the half-open ferrocene [(eta(5)-Pdl')Fe(eta(5)-Cp '')] (Cp '' = 1,2,4-(Me3C)(3)C5H2, 6) and mono(pentadienyl) iridium complex [(eta(5)-Pdl')Ir(eta(4)-cod)] (9) were successfully synthesized. The electronic and molecular structures of the half-open ferrocene [(eta(5)-Pdl')Fe(eta(5)-Cp '')] (6) and its closed analogue [(eta(5)-Cp')Fe(eta(5)-Cp '')] (7, Cp' = 1,3-(Me3C)(2)C5H3) were compared. Complex 6 is significantly more encumbered than 7, as shown by the short Pdl(cent)'-Fe distance. Clean oxidation of 6 and 7 can be accomplished electrochemically and chemically to give the half-open ferrocenium 6(+) and closed ferrocenium 7(+), respectively, and in both cases steric strain is released upon oxidation. On heating of 6(+) to 152 degrees C in the solid state H-2 and isobutene is eliminated to give [(eta(5)-Cp')(2)Fe](+) (8). (C) 2014 Elsevier B. V. All rights reserved.
• Synthesis and Reactivity of Sterically Encumbered Diazaferrocenes
  作者：Markus Kreye、Dirk Baabe、Peter Schweyen、Matthias Freytag、Constantin G. Daniliuc、Peter G. Jones、Marc D. Walter

  DOI：10.1021/om400474e

  日期：2013.10.28

  Bulky pyrrolyl ligands have been used for the synthesis of diazaferrocenes, which have been characterized by various spectroscopic techniques, including X-ray diffraction for rac-[eta(5)-2,3,5-(Me3C)(3)C4HN}(2)Fe]. Chemical oxidation of diazaferrocenes to the corresponding diazaferrocenium cations has been accomplished with AgSbF6. In addition, EPR and Mossbauer spectroscopic, electrochemical, and density function theory (DFT) studies have provided a more detailed understanding of the electronic structures of these complexes.
• The standard enthalpy of formation and low-temperature heat capacity of 1,1′,3,3′-tetra-(tert-butyl)ferrocene
  作者：M. S. Kozlova、V. N. Larina、N. V. Karyakin、M. S. Sheiman

  DOI：10.1134/s0036024408120029

  日期：2008.12

  The heat capacity of crystalline 1,1',3,3'-tetra-(tert-butyl) ferrocene (TTBF) was measured in an adiabatic vacuum calorimeter over the temperature range 5-302 K. The thermodynamic functions of TTBF in the crystalline state were calculated from T -> 0 to 302 K. The enthalpy of combustion of TTBF was determined in an isothermal calorimeter with a stationary bomb. The standard thermodynamic functions of formation of the compound in the crystalline state at 298.15 K were calculated.