bis(tert-butyl-η5-cyclopentadienyl)manganese | 101932-72-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: bis(tert-butyl-η5-cyclopentadienyl)manganese
• 英文别名: 5-Tert-butylcyclopenta-1,3-diene;manganese(2+)
• CAS: 101932-72-3
• 化学式: C₁₈H₂₆Mn
• 分子量: 297.342
• InChiKey: GCXWLNDTVZRRMY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  19
• 可旋转键数：
  2
• 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

反应信息

• 作为产物：
  描述：

  manganese(II) bromide 、 Magnesium;5-tert-butylcyclopenta-1,3-diene 以 四氢呋喃 为溶剂， 以42%的产率得到bis(tert-butyl-η5-cyclopentadienyl)manganese
  参考文献：
  名称：

  Spin Equilibria in Monomeric Manganocenes: Solid-State Magnetic and EXAFS Studies

  摘要：

  Magnetic susceptibility measurements and X-ray data confirm that tert-butyl-substituted manganocenes [(Me3C)(n)C5H5-n](2)Mn (n=1, 2) follow the trend previously observed with the methylated manganocenes; that is, electron-donating groups attached to the Cp ring stabilize the low-spin (LS) electronic ground state relative to Cp2Mn and exhibit higher spin-crossover (SCO) temperatures. However, introducing three CMe3 groups on each ring gives a temperature-invariant high-spin (HS) state manganocene. The origin of the high-spin state in [1,2,4-(Me3C)(3)C5H2](2)Mn is due to the significant bulk of the [1,2,4-(Me3C)(3)C5H2](-) ligand, which is sufficient to generate severe inter-ring steric strain that prevents the realization of the low-spin state. Interestingly, the spin transition in [1,3-(Me3C)(2)C5H3](2)Mn is accompanied by a phase transition resulting in a significant irreversible hysteresis (Delta T-c=16 K). This structural transition was also observed by extended X-ray absorption fine-structure (EXAFS) measurements. Magnetic susceptibility studies and X-ray diffraction data on SiMe3-substituted manganocenes [(Me3Si)(n)C5H5-n](2)Mn (n=1, 2, 3) show high-spin configurations in these cases. Although tetra- and hexasubstituted manganocenes are high-spin at all accessible temperatures, the disubstituted manganocenes exhibit a small low-spin admixture at low temperature. In this respect it behaves similarily to [(Me3C)-(Me3Si)C5H3](2)Mn, which has a constant low-spin admixture up to 90 K and then gradually converts to high-spin. Thermal spin-trapping can be observed for [(Me3C)(Me3Si)C5H3](2)Mn on rapid cooling.

  DOI：

  10.1021/om800922j

文献信息

• Electron spin adjustment in manganocenes. Preparative, paramagnetic NMR and X-ray study on substituent and solvent effects
  作者：Nikolaus. Hebendanz、Frank H. Koehler、Gerhard. Mueller、Juergen. Riede

  DOI：10.1021/ja00272a023

  日期：1986.6

  Preparation d'une serie de manganocenes ou l'on fait varier un substituant par Cp et le nombre d'alkyls par Cp. Etude RMN de la serie. Structure cristalline de (Me 3 SiCp) 2 Mn

  准备 d'une serie de manganocenes ou l'on fait varier un substituant par Cp et le nombre d'alkyls par Cp。练习曲 RMN de la 系列。结构 crastalline de (Me 3 SiCp) 2 Mn