(3-6-η-acetylcycloheptatriene)tricarbonyliron | 66615-42-7

• 英文名称: (3-6-η-acetylcycloheptatriene)tricarbonyliron
• 英文别名: {1-4-η-(5-acetyl)cycloheptatriene}iron tricarbonyl
• CAS: 66615-42-7
• 化学式: C₁₂H₁₀FeO₄
• 分子量: 274.056
• InChiKey: LNAJUDCFZUQAON-UHFFFAOYSA-N

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

反应信息

• 作为反应物：
  描述：

  (3-6-η-acetylcycloheptatriene)tricarbonyliron 以 甲醇 为溶剂， 以83%的产率得到{1-4-η-(6-acetyl)cycloheptatriene}iron tricarbonyl
  参考文献：
  名称：

  Isomerization pathways of (acylcycloheptatriene)iron tricarbonyl complexes

  摘要：

  The (7-exo-acylcycloheptatriene)Fe(CO)3 complexes (7-acyl) prepared by acylation of the mild organometallic nucleophile (eta(3)-C7H7)Fe(CO)3- isomerize readily to their 5-acyl and 6-acyl isomers. The 5-acyl isomer can be prepared in high yield by deprotonation of 7-acyl or 6-acyl followed by a proton quench. Refluxing 5- or 7-acyl in methanol gives the 6-acyl isomer. Rate studies have been carried out on the sequential isomerization of 7-acyl to 5-acyl to 6-acyl. Data were obtained by H-1 NMR monitoring in methanol-d4 at 40-degrees-C. The results indicate that both steps of the isomerization involve an intermolecular proton-exchange mechanism. Solvent deprotonation of any of the three acyl isomers gives a common conjugate base that can be reprotonated at three sites. Kinetic protonation gives 5-acyl, and thermodynamic protonation gives 6-acyl. Mass spectral analysis shows small but significant amounts of multiple deuterium incorporation, suggesting that the common anion intermediate can also be protonated at the metal to give a transient iron hydride.

  DOI：

  10.1021/om00037a058
• 作为产物：
  描述：

  {1-4-η-7-exo-acetylcycloheptatriene}iron tricarbonyl 在 potassium hydride 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 以72%的产率得到(3-6-η-acetylcycloheptatriene)tricarbonyliron
  参考文献：
  名称：

  Isomerization pathways of (acylcycloheptatriene)iron tricarbonyl complexes

  摘要：

  The (7-exo-acylcycloheptatriene)Fe(CO)3 complexes (7-acyl) prepared by acylation of the mild organometallic nucleophile (eta(3)-C7H7)Fe(CO)3- isomerize readily to their 5-acyl and 6-acyl isomers. The 5-acyl isomer can be prepared in high yield by deprotonation of 7-acyl or 6-acyl followed by a proton quench. Refluxing 5- or 7-acyl in methanol gives the 6-acyl isomer. Rate studies have been carried out on the sequential isomerization of 7-acyl to 5-acyl to 6-acyl. Data were obtained by H-1 NMR monitoring in methanol-d4 at 40-degrees-C. The results indicate that both steps of the isomerization involve an intermolecular proton-exchange mechanism. Solvent deprotonation of any of the three acyl isomers gives a common conjugate base that can be reprotonated at three sites. Kinetic protonation gives 5-acyl, and thermodynamic protonation gives 6-acyl. Mass spectral analysis shows small but significant amounts of multiple deuterium incorporation, suggesting that the common anion intermediate can also be protonated at the metal to give a transient iron hydride.

  DOI：

  10.1021/om00037a058

文献信息

• Reaction of tricarbonyliron complexes of some cycloheptatrienes with tetracyanoethylene, sulphur dioxide, and protons
  作者：Desmond Cunningham、Patrick McArdle、Hal Sherlock、Brian F. G. Johnson、Jack Lewis

  DOI：10.1039/dt9770002340

  日期：——

  reversible 1 : 1 adduct with sulphur dioxide. The adductand other tricarbonyliron complexes with the σ, η3 mode of bonding exhibit small Mössbauer quadrupole splittings. Tetracyanoethylene undergoes 1,3-addition to the unco-ordinated side of the ring of both the 1- and 2-acetyl derivatives of (1), whereas the proton adds to the co-ordinated double bond of the 2-acetyl derivative.

  三羰基（3–6-η-环庚三烯）铁（1）与二氧化硫形成可逆的1：1加合物。与σ的adductand其他tricarbonyliron络合物，η 3接合表现出小穆斯堡尔四极分裂的模式。四聚氨基乙烯在（1）的1-和2-乙酰基衍生物的环的未配位侧进行1,3-加成，而质子则在2-乙酰基衍生物的配位双键上加成。
• The rate and mechanism of tetracyanoethylene addition of cycloheptatriene and related complexes of tricarbonyliron
  作者：Suman K. Chopra、Michael J. Hynes、Patrick McArdle

  DOI：10.1039/dt9810000586

  日期：——

  the 1,3-addition of tetracyanoethylene to a range of substituted cycloheptatriene complexes have been measured. Mechanisms are proposed for the addition reactions. The results suggest that tricarbonyliron is activating and that neither ionic nor free radical intermediates are involved. The 1-formylcycloheptatriene complex was found to undergo two parallel reactions. A rapid but reversible 1,3-addition

  已经测量了四氰基乙烯向一系列取代的环庚三烯配合物的1，3-加成的速率常数。提出了加成反应的机理。结果表明三羰基铁正在活化，并且离子或自由基中间体均不参与。发现1-甲酰基环庚三烯络合物经历两个平行反应。快速但可逆的1,3-加成与慢得多但不可逆的4,6-加成竞争。