(η5-(methoxycarbonyl)cyclopentadienyl)(η4-tetrakis(methylthio)cyclobutadiene)cobalt(I) | 786691-02-9

• 英文名称: (η5-(methoxycarbonyl)cyclopentadienyl)(η4-tetrakis(methylthio)cyclobutadiene)cobalt(I)
• CAS: 786691-02-9
• 化学式: C₁₅H₁₉CoO₂S₄
• 分子量: 418.572
• InChiKey: HMYSTDSBGMSCPS-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：

  (η5-(methoxycarbonyl)cyclopentadienyl)(η4-tetrakis(methylthio)cyclobutadiene)cobalt(I) 、 一氧化碳 以 萘烷 为溶剂， 以54%的产率得到(η5-(methoxycarbonyl)cyclopentadienyl)(η4-tetrakis(methylthio)cyclopentadienone)cobalt(I)
  参考文献：
  名称：

  CpCo-Stabilized Cyclopentadienones from Cyclobutadiene Complexes:  Experimental and Theoretical Investigations

  摘要：

  The reaction of 1,4,8,11-tetrathiacyclotetradeca-2,9-diyne (7) with C5H4(CO2Me)Co(CO)(2) (8) and C5H4(SiMe3)Co(CO)(2) (10) led to the tricyclic cyclopentadienone complexes 9 and 11. In both species the CO was inserted into a former triple bond. This observation led to the preparation of the tetrathiaalkyl- and tetrathiaaryl-substituted C5H4(CO2Me)Co-capped cyclobutadiene complexes 23 and 27-30. When these compounds were heated under a pressurized CO atmosphere at 170 degrees C, the corresponding cyclopentadienone complexes 9, 15, and 31-33 were formed. Model calculations at the B3LYP level of theory on tetrasubstituted (R = CH3, SH, (CH2)(3), S-CH2-S) CpCo-capped cyclobutadiene complexes showed that the substitution, especially by SH and S-CH2-S, considerably lowered the energy of the assumed intermediate metallacycles 35 and 36, which opens the possibility of reaction.

  DOI：

  10.1021/om050048r
• 作为产物：
  描述：

  1,2-双(甲硫基)乙炔 、 dicarbonyl(η(5)-methoxycarbonylcyclopentadienyl)cobalt 以 甲苯 为溶剂， 生成 (η5-(methoxycarbonyl)cyclopentadienyl)(η4-tetrakis(methylthio)cyclobutadiene)cobalt(I)
  参考文献：
  名称：

  CpCo-Stabilized Cyclopentadienones from Cyclobutadiene Complexes:  Experimental and Theoretical Investigations

  摘要：

  The reaction of 1,4,8,11-tetrathiacyclotetradeca-2,9-diyne (7) with C5H4(CO2Me)Co(CO)(2) (8) and C5H4(SiMe3)Co(CO)(2) (10) led to the tricyclic cyclopentadienone complexes 9 and 11. In both species the CO was inserted into a former triple bond. This observation led to the preparation of the tetrathiaalkyl- and tetrathiaaryl-substituted C5H4(CO2Me)Co-capped cyclobutadiene complexes 23 and 27-30. When these compounds were heated under a pressurized CO atmosphere at 170 degrees C, the corresponding cyclopentadienone complexes 9, 15, and 31-33 were formed. Model calculations at the B3LYP level of theory on tetrasubstituted (R = CH3, SH, (CH2)(3), S-CH2-S) CpCo-capped cyclobutadiene complexes showed that the substitution, especially by SH and S-CH2-S, considerably lowered the energy of the assumed intermediate metallacycles 35 and 36, which opens the possibility of reaction.

  DOI：

  10.1021/om050048r

文献信息

• Donor-substituted CpCo-stabilized cyclobutadienes and superphanes
  作者：Daniel B. Werz、J. Hilko Schulte、Rolf Gleiter、Frank Rominger

  DOI：10.1016/j.jorganchem.2004.06.048

  日期：2004.9

  RCpCoL2 complexes (L-2 = (CO)(2) or COD, R = H, CO2Me, TMS) were reacted with various alkynes substituted with chalcogen atoms adjacent to the triple bonds. These reactions yielded hetero-substituted CpCo-capped cyclobutadienes and superphanes dependent on the ring size of the corresponding cyclic diene used as starting material. Reactions in decaline afforded not only CpCo-capped cyclobutadieno superphanes, but also mixed cyclobutadieno cyclopentadienono superphanes. X-ray analyses do not indicate a significant amount of conjugation between the pi systems and the lone pairs of the heteroatoms whereas cyclic voltammetry reveals an easier oxidation when increasing the number of electron-donating heteroatoms. (C) 2004 Elsevier B.V. All rights reserved.