(η5-methylcyclopentadienyl)iron carbonyl tetramer | 144497-13-2

• 英文名称: (η5-methylcyclopentadienyl)iron carbonyl tetramer
• 英文别名: [(η5-methylcyclopentadienyl)4Fe4(μ3-CO)4]；(η5-C5H4Me)4Fe4(μ3-CO)4；(η5-C5H4Me)4Fe4(CO)4
• CAS: 144497-13-2
• 化学式: C₂₈H₂₈Fe₄O₄
• 分子量: 651.916
• InChiKey: QPKMQCJDIHPVER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 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-methylcyclopentadienyl)iron carbonyl tetramer 、 lithium aluminium tetrahydride 以 四氢呋喃 为溶剂， 以77%的产率得到[(η5-methylcyclopentadienyl)4Fe4(μ4-η2:η2:η1:η1-HCCH)2]
  参考文献：
  名称：

  Synthesis and Structures of One- and Two-Electron Oxidized Forms of Bis(acetylene)tetrairon Clusters Cp‘₄Fe₄(HCCH)₂ (Cp‘ = Cp, η⁵-C₅H₄Me)

  摘要：

  Air-oxidation of Cp'Fe-4(4)(HCCH)(2) (Cp' = Cp (1a), C5H4Me (1b)) in an NH4PF6/CH3CN solution afforded the one-electron oxidized clusters [Cp'Fe-4(4)(HCCH)(2)](PF6). Oxidation of 1a with excess AgBF4 in THF afforded [1a](BF4), while that of 1b with excess AgBF4 gave [1b](BF4)(2). The X-ray crystal structure analysis of [1a](BF4) revealed that the monocationic cluster retains the butterfly-type Fe-4(mu(4)-eta(2):eta(2):eta(1):eta(1)-HCCH)(2) framework similar to that of the neutral cluster. The average Fe-Fe bond length is shorter by 0.029 Angstrom than that in the neutral cluster. Electrochemical oxidation of 1a and 1b in 0.1 M NH4PF6/CH3CN solution at +0.30 and +0.25 V versus Ag/10 mM AgNO3, respectively, afforded the two-electron oxidized clusters [1a](PF6)(2) and [1b](PF6)(2). The X-ray crystal structure analysis for [1b]-(BF4)(2) shows that the butterfly-type cluster core is retained but shrinks more of those of neutral and monocationic clusters. The four Fe-Fe bonds in [1b](BF4)(2) are unequivalent: one Fe-Fe bond (2,397(1) Angstrom) is apparently shorter than the others (2.439(2)-2.461(2) Angstrom).

  DOI：

  10.1021/ic025763x
• 作为产物：
  描述：

  [(η(5)-CH3C5H4)Fe(CO)2]2 在 triphenyl phosphine 作用下， 以 xylene 为溶剂， 生成 (η5-methylcyclopentadienyl)iron carbonyl tetramer
  参考文献：
  名称：

  Picosecond investigations of the excited-state transition at 532 nm in King's complex [(C5H5)Fe(CO)]4 and synthesized analogs

  摘要：

  Variations of the organometallic cluster known as King's complex, [(C5H5)Fe(CO)]4, have been synthesized to study the excited-state transition responsible for reverse saturable absorption observed at 532 nm in this molecule. Picosecond pump-probe measurements have been used to measure the excited-state cross sections and lifetimes in King's complex and the analogs methyl-King's complex, [CH3(C5H4)Fe(CO)]4, and triethylaluminum King's complex, [(C5H5) Fe{COAl(C2H5)3}]4. Within experimental error, the excited-state parameters are unaffected by alterations to either the carbonyl or the cyclopentadienyl ligand of the King's complex. These results are consistent with an excited-state absorption resulting from a second d to d transition within the singlet states of the metal core.

  DOI：

  10.1021/j100052a036

文献信息

• Reversible Cleavage and Recombination of an Acetylenic Carbon−Carbon Bond on a Tetrairon Cluster Coupled with a Two-Electron Redox Reaction
  作者：Masaaki Okazaki、Takeo Ohtani、Hiroshi Ogino

  DOI：10.1021/ja049720m

  日期：2004.4.1

  Two-electron reduction of [(eta5-C5H4Me)4Fe4(mu3-CH)2(mu3-CO)2](PF6)2 (1) results in the coupling of two methylidyne ligands to form (eta5-C5H4Me)4Fe4(HCCH)(mu3-CO)2 (2), the two-electron oxidation of which reproduces 1. Structures of 1 and 2 were determined by X-ray diffraction analysis.

  [(eta5-C5H4Me)4Fe4(mu3-CH)2(mu3-CO)2](PF6)2 (1) 的双电子还原导致两个亚甲基配体偶联形成 (eta5-C5H4Me)4Fe4(HCCH) )(mu3-CO)2 (2)，其二电子氧化再现1。1和2的结构通过X射线衍射分析确定。
• Stepwise Reduction of Four Carbonyl Ligands in (η⁵-C₅H₄Me)₄Fe₄(μ₃-CO)₄ To Produce Clusters Containing μ₃-Methylidyne and/or Acetylene Ligands
  作者：Masaaki Okazaki、Takeo Ohtani、Masato Takano、Hiroshi Ogino

  DOI：10.1021/om049606c

  日期：2004.8.1

  Treatment of (eta(5)-C5H4Me)(4)Fe-4(mu(3)-CO)(4) with LiAlH4, followed by air-oxidation in the presence of NH4PF6, led to stepwise reduction of the four carbonyl ligands to afford [(eta(5)-C5H4Me)(4)Fe-4(mu(3)-CO)(3)(mu(3)-CH)](PF6), [(eta(5)-C5H4Me)(4)Fe-4(mu(3)-CO)(2)(mu(3)-CH)(2)](PF6)(2), [(eta(5)-C5H4Me)(4)Fe-4(mu(3)-CO)(mu(3)-CH)(HCCH)]PF6), and [(eta(5)-C5H4Me)(4)Fe-4(HCCH)(2)](PF6). Two-electron reduction of [(eta(5)-C5H4Me)(4)Fe-4(mu(3)-CO)(2)(mu(3)-CH)(2)](PF6)(2) resulted in coupling of two methylidyne ligands to form the acetylene-coordinated cluster (eta(5)-C5H4Me)(4)Fe-4(mu(3)-CO)(2)(HCCH), two-electron oxidation of which regenerated [(eta(5)-C5H4Me)(4)Fe-4(mu(3)-CO)(2)(mu(3)-CH)(2)](PF6)(2). Further treatment of isolated (eta(5)-C5H4Me)(4)Fe-4(mu(3)-CO)(2)(HCCH) with LiAlH4 produced (eta(5)-C5H4Me)(4)Fe-4(HCCH)(2). All clusters were fully characterized by X-ray diffraction studies.