Fe(κ2-dppe)(η5-C5Me5){C≡C(1,4-C6H4)C≡CSiMe3} | 557790-37-1

• 英文名称: Fe(κ2-dppe)(η5-C5Me5){C≡C(1,4-C6H4)C≡CSiMe3}
• 英文别名: Fe(κ²-dppe)(η⁵-C₅Me₅){C≡C(1,4-C₆H₄)C≡CSiMe₃}；[(η2-1,2-bis(diphenylphosphino)ethane)(η5-C5Me5)FeCC(1,4-(C6H4)-C2-SiMe3)]
• CAS: 557790-37-1
• 化学式: C₄₉H₅₂FeP₂Si
• 分子量: 786.832
• InChiKey: BAFGBQULCNFSRY-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：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Fe(κ2-dppe)(η5-C5Me5){C≡C(1,4-C6H4)C≡CSiMe3} 在 甲醇 、 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以85%的产率得到Fe(κ2-dppe)(η5-C5Me5){C≡C(1,4-C6H4)C≡CH}
  参考文献：
  名称：

  Synthesis and Characterization of Redox-Active Mononuclear Fe(κ²-dppe)(η⁵-C₅Me₅)-Terminated π-Conjugated Wires

  摘要：

  Several new redox-active Fe(kappa(2)-dppe)(eta(5)-C5Me5) arylacetylide complexes featuring pendant ethynyl (Fe(kappa(2)-dppe)(eta(5)-C5Me5)-[{C equivalent to C(1,4-C6H4)}(n)C equivalent to CH] (1b-d; n = 1-3), Fe(kappa(2)-dppe)(eta(5)-C5Me5)[C equivalent to C(1,3-C6H4)C equivalent to CH] (2)) or ethenyl (Fe(kappa(2)-dppe)(eta(5)-C5Me5)[CE equivalent to C(1,4-C6H4)CH equivalent to CH2] (3)) groups have been synthesized and characterized under their Fe(II) and Fe(III) states. In contrast to the known ethynyl Fe(III) complex [Fe(kappa(2)-dppe)(eta(5)-C5Me5)(C7 equivalent to CH)][PF6] (1a[PF6]), most of the new Fe(III) derivatives turned out to be kinetically stable in solution. A consistent picture of the electronic structure of the latter complexes in both redox states emerged from experimental data and DFT calculations. This study revealed that beyond the first 1,4-phenylene ring, modification or extension of the carbon-rich linker using (4-phenylene)ethynylene spacers will have only a minor influence on their electronic properties in their ground state, while still maintaining some (weak) electronic interaction along the carbon-rich backbone.

  DOI：

  10.1021/om400515g
• 作为产物：
  描述：

  在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以536 mg的产率得到Fe(κ2-dppe)(η5-C5Me5){C≡C(1,4-C6H4)C≡CSiMe3}
  参考文献：
  名称：

  Synthesis and Characterization of Redox-Active Mononuclear Fe(κ²-dppe)(η⁵-C₅Me₅)-Terminated π-Conjugated Wires

  摘要：

  Several new redox-active Fe(kappa(2)-dppe)(eta(5)-C5Me5) arylacetylide complexes featuring pendant ethynyl (Fe(kappa(2)-dppe)(eta(5)-C5Me5)-[{C equivalent to C(1,4-C6H4)}(n)C equivalent to CH] (1b-d; n = 1-3), Fe(kappa(2)-dppe)(eta(5)-C5Me5)[C equivalent to C(1,3-C6H4)C equivalent to CH] (2)) or ethenyl (Fe(kappa(2)-dppe)(eta(5)-C5Me5)[CE equivalent to C(1,4-C6H4)CH equivalent to CH2] (3)) groups have been synthesized and characterized under their Fe(II) and Fe(III) states. In contrast to the known ethynyl Fe(III) complex [Fe(kappa(2)-dppe)(eta(5)-C5Me5)(C7 equivalent to CH)][PF6] (1a[PF6]), most of the new Fe(III) derivatives turned out to be kinetically stable in solution. A consistent picture of the electronic structure of the latter complexes in both redox states emerged from experimental data and DFT calculations. This study revealed that beyond the first 1,4-phenylene ring, modification or extension of the carbon-rich linker using (4-phenylene)ethynylene spacers will have only a minor influence on their electronic properties in their ground state, while still maintaining some (weak) electronic interaction along the carbon-rich backbone.

  DOI：

  10.1021/om400515g

文献信息

• Versatile reactions of a para-bromophenylacetylide iron(II) derivative and X-ray structure of the fluoro analogue.
  作者：James Courmarcel、Gildas Le Gland、Loic Toupet、Frédéric Paul、Claude Lapinte

  DOI：10.1016/s0022-328x(02)02137-x

  日期：2003.3

  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.