[(η2-1,2-bis(diphenylphosphino)ethane)(η5-C5Me5)FeCC(1,3-(C6H4)F)] | 557790-34-8

• 英文名称: [(η2-1,2-bis(diphenylphosphino)ethane)(η5-C5Me5)FeCC(1,3-(C6H4)F)]
• 英文别名: (η2-Ph2PCH2CH2PPh2)(η5-C5Me5)Fe-CC-C6H4-3-F；(η2-dppe)(η5-C5Me5)Fe-C.ident.C-3-(C6H4)F
• CAS: 557790-34-8
• 化学式: C₄₄H₄₃FFeP₂
• 分子量: 708.618
• InChiKey: XKEYQUTZOCUZSS-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：
  None
• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  ferrocenium hexafluorophosphate 、 [(η2-1,2-bis(diphenylphosphino)ethane)(η5-C5Me5)FeCC(1,3-(C6H4)F)] 以 二氯甲烷 为溶剂， 以78%的产率得到[(η2-dppe)(η5-C5Me5)Fe-C.ident.C-3-(C6H4)F][PF6]
  参考文献：
  名称：

  电子富铁（III）钢琴凳σ-乙炔化物中的自旋离域化。实验（NMR）和理论（DFT）研究

  摘要：

  几个顺富电子的Fe（III）的单核arylacetylide式的配合物[（η 2 -dppe）（η 5 -C 5我5）的Fe（C⋮C-AR）] +其中Ar表示官能的芳基进行了研究通过多核NMR。分配了检测到的各个核的所有信号。芳基乙炔配体的选定核的超精细偶合常数源自1 H或19 F NMR接触位移。根据DFT计算，这些NMR数据可诊断出部分位于芳基乙炔配体上π分子轨道上的金属中心不成对电子。我们在这里表明邻位的1 H NMR顺磁位移（H1）和间（H 2）芳基乙炔质子传递有关芳基环中电荷分布的决定性信息。还从1 H NMR信号的半宽得出未配对电子的弛豫率。最后，对Fe（II）/ Fe（III）混合物进行了广泛的研究，可以提取这些配合物中几种氧化还原对的自交换速率。对于在芳基环上具有吸电子取代基的化合物，自交换速率似乎略微依赖于取代基，并且显然更大。重组能量约。对于这些外层电子转移过程，可以得出4000

  DOI：

  10.1021/om060989j
• 作为产物：
  描述：

  (η(2)-1,2-bis(diphenylphosphino)ethane)(η(5)-pentamethylcyclopentadienyl)Fe-C.tplbond.CH 、 间溴氟苯 在 catalyst: Pd(PPh₃)2Cl₂/CuI 作用下， 以 further solvent(s) 为溶剂， 以74%的产率得到[(η2-1,2-bis(diphenylphosphino)ethane)(η5-C5Me5)FeCC(1,3-(C6H4)F)]
  参考文献：
  名称：

  Versatile reactions of a para-bromophenylacetylide iron(II) derivative and X-ray structure of the fluoro analogue.

  摘要：

  The synthesis of the new (eta(2)-dppe)(n(5)-C5Me5)Fe-CdropC-1,3-(C6H4X) (m-2a/2b; X = F/Br) and (n(2)-dppe)(eta(5)-C5Me5)Fe-CdropC-1,4-(C6H4F) (2a) (2c) complexes, as well as the solid-state structure of the known (eta(2)-dppe)(eta(5)-C5Me5)Fe-CdropC-1,4-(C6H4F) (2a) complex are described. The catalytic coupling reactions of the bromo complexes with various alkynes were next investigated. Starting from the known (eta(2)-dppe)(eta(5)-C5Me5)Fe-CdropC-1,4-(C6H4Br) complex (2b), the synthesis of the (eta(2)-dppe)(eta(5)-C5Me5)FeCdropC-1,4-(C6H4)-CdropC-H complex (6d) and of the corresponding silyl-protected precursors (eta(2)-dppe)(eta(5)-C5Me5)Fe-CdropC-1,4-(C6H4)CdropC-SiR3 (6b/6c; R = Pr-1/Me) are reported. By use of lithium-bromine exchange reactions on 2b, the silyl-(7a; E = Si; R = Me) and tin- (7b-7d; E = Sn; R = Me, Bu, Ph) substituted analogues (eta(2)-dppe)(eta(5)-C5Me5)Fe-CdropC-1,4-(C6H4)ER3 are also isolated. The spectroscopic and electrochemical characterisations of all these new Fe(II)/Fe(III) redox-active building blocks are presented and the electronic substituent parameters for the ''(eta(2)-dppe)(eta(5)-C5Me5)Fe-CdropC" group are determined by means of F-19-NMR. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)02137-x

文献信息

• One-Pot Synthesis of Mononuclear Iron Alkynyl Complexes by Photolysis
  作者：Gilles Argouarch、Guillaume Grelaud、Frédéric Paul

  DOI：10.1021/om100665u

  日期：2010.10.11

  A new access to organoiron complexes of type (dppe)Cp*Fe-C C- Ar the easily prepared precursor (CO)(2)Cp*FeCl (5) is de.vcribed. This direct one-pot transformation realized upon UV irradiation is illustrated by various aromatic alkynes. A mechanism is also proposed for this reaction via the key intermediate[dppe)Cp*Fe(CO)][PF6](6).