2,5-diferrocenyl-1-phenyl-1H-phosphole | 1432754-15-8

• 英文名称: 2,5-diferrocenyl-1-phenyl-1H-phosphole
• 英文别名: 2,5-diferrocenyl-1-phenyl-1H-phospnole
• CAS: 1432754-15-8
• 化学式: C₃₀H₂₅Fe₂P
• 分子量: 528.196
• InChiKey: ZJMVNKDPQSSTJU-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：

  2,5-diferrocenyl-1-phenyl-1H-phosphole 在 selenium 作用下， 以 二氯甲烷 为溶剂， 以86%的产率得到2,5-diferrocenyl-1-phenyl-1H-phosphole selenide
  参考文献：
  名称：

  合成和（分光）的2,5-茂铁-1-苯基-1-的电化学行为ħ -phosphole

  摘要：

  通过苯基膦与1，4-二茂铁基丁二炔的环化反应已成功地制备了2，5-二茂铁基-1-苯基-1 H-磷（3）。随后分别与元素硫和硒反应，导致形成适当的磷硫化物（4）或硒化物（5）。分子4和5在结构上已通过单晶X射线衍射表征。尽管磷原子处于四面体环境，但c C 4P环本身是平面的并且与二茂铁基末端的环戊二烯基环共面。电化学测量表明，两个二茂铁基团可以在离散电势下被氧化，分别的氧化还原波分别为280（3），240（4）和235 mV（5）。这些值与杂环桥联的二铁茂铁基化合物的其他实例一致，例如二铁茂铁基噻吩（260 mV）和二铁茂铁基呋喃（290 mV）。化合物[ 3 ] + – [ 5 ] +表现出弱到中等强度的IVCT吸收，这与弱耦合混合价系统的Hush两种状态模型的预测非常吻合。这些结论得到DFT和TD-DFT结果的支持，这些结果可以令人满意地对观察到的结构和光谱参数进行建模。计算工作有助于分

  DOI：

  10.1021/om400201b
• 作为产物：
  描述：

  1,4-bis(ferrocenyl)-1,3-butadiyne 、 苯基膦 在 正丁基锂 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 12.17h， 以52%的产率得到2,5-diferrocenyl-1-phenyl-1H-phosphole
  参考文献：
  名称：

  合成和（分光）的2,5-茂铁-1-苯基-1-的电化学行为ħ -phosphole

  摘要：

  通过苯基膦与1，4-二茂铁基丁二炔的环化反应已成功地制备了2，5-二茂铁基-1-苯基-1 H-磷（3）。随后分别与元素硫和硒反应，导致形成适当的磷硫化物（4）或硒化物（5）。分子4和5在结构上已通过单晶X射线衍射表征。尽管磷原子处于四面体环境，但c C 4P环本身是平面的并且与二茂铁基末端的环戊二烯基环共面。电化学测量表明，两个二茂铁基团可以在离散电势下被氧化，分别的氧化还原波分别为280（3），240（4）和235 mV（5）。这些值与杂环桥联的二铁茂铁基化合物的其他实例一致，例如二铁茂铁基噻吩（260 mV）和二铁茂铁基呋喃（290 mV）。化合物[ 3 ] + – [ 5 ] +表现出弱到中等强度的IVCT吸收，这与弱耦合混合价系统的Hush两种状态模型的预测非常吻合。这些结论得到DFT和TD-DFT结果的支持，这些结果可以令人满意地对观察到的结构和光谱参数进行建模。计算工作有助于分

  DOI：

  10.1021/om400201b

文献信息

• Influence of P‐Bonded Bulky Substituents on Electronic Interactions in Ferrocenyl‐Substituted Phospholes
  作者：Dominique Miesel、Alexander Hildebrandt、Marcus Korb、Duncan A. Wild、Paul J. Low、Heinrich Lang

  DOI：10.1002/chem.201501188

  日期：2015.8.3

  radical cations. Monocationic [3 b]+–[3 e]+ show intervalence charge‐transfer absorptions between 4650 and 5050 cm−1 of moderate intensity and half‐height bandwidth. Compounds 3 c–e with bulky, electron‐rich substituents reveal a significant increase in electronic interactions compared with less demanding groups in 3 a and 3 b.

  2,5-茂铁-1-的Ar-1 ħ -phospholes 3 - ë（AR =苯基（一），二茂铁基（b），三甲苯基（Ç），2,4,6-三苯基苯基（d），和图2， 4,6-三-叔丁基苯基（é））已通过ArPH的反应制备2（1 - Ë与1,4-丁二茂铁）。化合物3b – e在结构上已通过单晶XRD分析进行了表征。的空间要求-2,4,6-三中的应用叔‐丁基苯基基团导致锥体磷环境的扁平化增加。二茂铁基单元可以单独氧化，在[N n Bu 4 ] [B（C 6 F ）中的氧化还原间隔为265（3 b），295（3 c），340（3 d）和315 mV（3 e）。5）4 ]; 这些值表明混合价自由基阳离子具有显着的热力学稳定性。单阳离子[ 3 b ] + – [ 3 e ] +在4650至5050 cm -1之间显示间隔电荷转移吸收具有中等强度和半高带宽。与3a和3b中要求较低的基团相比，具有庞大的富电子取代基的化合物3c
• Transition-Metal Carbonyl Complexes of 2,5-Diferrocenyl-1-phenyl-1<i>H</i>-phosphole
  作者：Dominique Miesel、Alexander Hildebrandt、Marcus Korb、Dieter Schaarschmidt、Heinrich Lang

  DOI：10.1021/acs.organomet.5b00520

  日期：2015.9.14

  Pentacarbonyl(2,5-diferro cenyl-1-phenyl-1Hphosphole)metal complexes 3a-c (3a, M = Cr; 3b, M = Mo; 3c, M = W) have successfully been synthesized by the reaction of 2,5-diferrocenyl-1-phenyl-1H-phosphole (1) with M(CO)(5)(thf) (2a, M = Cr; 2b, M = Mo; 2c, M = W). Further irradiation of 3a-c with 1 equiv of 1 in tetrahydrofuran leads to tetracarbonylbis (2,5 - diferrocenyl-1-phenyl-1H-phosphole)metal complexes 4a-c (4a, M = Cr; 4b, M = Mo; 4c, M = W). In addition, the reaction of 1 with Fe2(C0)9 gave tetracarbonyl(2,5-diferrocenyl-1-phenyl-1H-phosphole)iron (6) and heptacarbonyl [mu- (2,3,4-eta)-1- (2,5- diferro cenyl-1-phenyl-1H-phosphole) diiron (7), respectively. Treatment of 2,5-diferrocenyl- 1-phenyl- 1H-phosphole sulfide ( 8) with Fe-2 (CO)(9) afforded tricarbonyl[(2,3,4,5-eta)-(2,5-diferrocenyl-1-phenyl-1H-phosphole 1-sulfide)]iron (9). Complexes 3b,c, 4c, 7, and 9 have been characterized by single-crystal X-ray diffraction. Molecules 3b,c and 4c exhibit a distorted-octahedral geometry, whereas in 4c the two phosphole units are cis-oriented. Coordination of the dienic system to Fe(C0)3 in 7 and 9, respectively, resulted in a deflection of the phosphorus atom from the C-4 plane. Electrochemical measurements of 3a-c, 4a-c, and 9 demonstrated that the ferrocenyl units can be oxidized separately. The coordination of the dienic system to the Fe(C0)3 building block leads to a decrease of the redox splitting (Delta E degrees' = 190 mV) in comparison to 8 (Delta E degrees' = 240 mV). Mixed-valence [3a-c](+), [4a-c](2+), and [9](+) show IVCT absorptions of weak to moderate strengths. The coordination of the phosphorus atom to M(CO)5 in 3a-c has no significant influence on the metal-metal interaction in the mixed-valent species. However, the coordination of the dienic system in 9 results in a significantly decreased electronic communication of the Pc/Fe termini -via the heterocyclic core.
• Electronic interactions in gold(I) complexes of 2,5-diferrocenyl-1-phenyl-1H-phosphole
  作者：Dominique Miesel、Alexander Hildebrandt、Marcus Korb、Heinrich Lang

  DOI：10.1016/j.jorganchem.2015.12.014

  日期：2016.2

  The synthesis of gold(I) complexes of 2,5-diferrocenyl-1-phenyl-1H-phosphole (1) is presented. Chloro(2,5-diferrocenyl-1-phenyl-1H-phosphole) gold (3) has successfully been prepared by the reaction of 1 with AuCl(SMe2) (2). Treatment of 2 with arylethyne (aryl = ferrocenyl, phenyl) using catalytical amounts of [CuI] and 1 equiv. of 1 gave arylethynyl-(2,5-diferrocenyl-1-phenyl-1H-phosphole)gold 4a and 4b (aryl: a = ferrocenyl; b = phenyl). Compound [mu-(1,4-phenylenedi-2,1-ethynediyl)]bis(2,5-diferrocenyl-1-phenyl-1H-phosphole)digold (5) could be synthesized by a similar procedure using 0.5 equiv. of 1,4-diethynylbenzene. The electrochemical properties of 3, 4a, b and 5 were investigated by cyclic and square wave voltammetry. In 3, 4a and 4b each ferrocenyl unit shows one reversible redox event with redox separations of the ferrocenyl moieties in 2,5 position of approximately 260 mV. In 5 two redox events for the four ferrocenyl groups were observed. Spectroelectrochemical measurements of 3, 4a and 4b reveal IVCT absorptions with intensities of 1100-1300 L mol(-1) cm(-1) and a full-width-at-half-height of approximate to 3650 cm(-1). In 5 two mixed-valent units are present per molecule and therefore, the intensity of the IVCT band is increased to 2700 L mol(-1) cm(-1). Compounds 3, 4a, b and 5 can be classified as moderately coupled class II systems according to Robin and Day. The complexation of the gold(I) fragment by the phosphorus atom leads to a decreased metal-metal interaction when compared to 1. (C) 2015 Elsevier B.V. All rights reserved.