sodium (pentafluorophenyl)cyclopentadienide | 184481-02-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: sodium (pentafluorophenyl)cyclopentadienide
• 英文别名: sodium (pentafluorophenyl)cyclopenadienide；sodium pentafluorophenylcyclopentadienide；Sodium 1-(pentafluorophenyl)cyclopenta-2,4-dien-1-ide；sodium;1-cyclopenta-2,4-dien-1-yl-2,3,4,5,6-pentafluorobenzene
• CAS: 184481-02-5
• 化学式: C₁₁H₄F₅*Na
• 分子量: 254.135
• InChiKey: BJQUHVBRESCJQF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.77
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  五羰基溴化锰(I) 、 sodium (pentafluorophenyl)cyclopentadienide 以 四氢呋喃 为溶剂， 以67%的产率得到tricarbonyl[η(5)-pentafluorophenylcyclopentadienyl]manganese(I)
  参考文献：
  名称：

  五氟苯基取代基对Fe，Co，Mn和Re 1的环戊二烯基配合物的结构和电子效应

  摘要：

  CpNa（Cp = C 5 H 5）与C 6 F 6（二甘醇二甲醚，110°C，14 h）反应生成了一种产物混合物，其中有两种新的三芳基环戊二烯1,2,4-Ar 3 C 5通过硅胶色谱法（Ar ＝ C 6 F 5）分离出H 3（3）和1,2,3-Ar 3 C 5 H 3（4）。二烯3和4易于转化（NaH，THF）转化为相应的三芳基环戊二烯化钠（1,2,4-Ar 3 C 5 H2）Na（7）和（1,2,3-Ar 3 C 5 H 2）Na（8）。配体7和8与FeBr 2的反应得到二茂铁（1,2,4-Ar 3 C 5 H 2）2 Fe（11）和（1,2,3-Ar 3 C 5 H 2）2 Fe（12）。钴烯（ArC 5 H 4）2 Co（13），（1,3-Ar 2 C 5H 3）2 Co（14），（1,2,4-Ar 3 C 5 H 2）2 Co（15）和（1,2,3-Ar 3 C 5 H 2）2 Co（16）为分别由CoBr

  DOI：

  10.1021/om000798v
• 作为产物：
  描述：

  六氟苯 、 sodium cyclopentadienide 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 sodium (pentafluorophenyl)cyclopentadienide
  参考文献：
  名称：

  Ligand Synthesis

  摘要：

  化合物1,3,4-(SiMe3)(C6F5)(烷基)C5H3使用一种简化的合成策略制备，该策略易于扩大规模。与适当的过渡金属物种反应时，1,3,4-(SiMe3)(C6F5)(烷基)C5H3分子提供了一种有机过渡金属配合物，其中包含一个1,2-(C6F5)(烷基)取代的环戊二烯基配体，对烯烃聚合具有活性。

  公开号：

  US20130310590A1

文献信息

• The formation and polymerization behavior of (pentafluorophenyl)-cyclopentadienyl titanium compounds
  作者：Richard J. Maldanis、James C.W. Chien、Marvin D. Rausch

  DOI：10.1016/s0022-328x(99)00742-1

  日期：2000.4

  olefins. The half-sandwich complex 2 is formed by reaction of a trimethylsilyl intermediate with TiCl4. Similarly, the metallocene complex 4 is formed by reaction of a trimethyltin intermediate with TiCl4. EPR measurements of 2/methylaluminoxane (MAO) and 4/MAO in toluene solution indicate facile reduction to Ti(III) species occurs. It is suggested that the titanium complexes 2 and 4 with electron-withdrawing

  合成了[C 5 H 4（C 6 F 5）] CpTiCl 3（2）和[C 5 H 4（C 6 F 5）] 2 TiCl 2（4），并与[C 5 H 4（C）进行了比较。6 F 5）] 2 ZrCl 2（5），CpTiCl 3，Cp 2 TiCl 2和Cp 2 ZrCl 2聚合烯烃的能力。半三明治复合物2是通过三甲基甲硅烷基中间体与TiCl 4反应形成的。类似地，茂金属配合物4是通过三甲基锡中间体与TiCl 4反应形成的。甲苯溶液中2 /甲基铝氧烷（MAO）和4 / MAO的EPR测量表明，容易还原为Ti（III）物种。建议具有吸电子五氟苯基取代基的钛配合物2和4在聚合过程中有利于还原。这将解释2中观察到的高活性和立体规律性。苯乙烯的活性较差，乙烯为4。通常，锆化合物的还原电位比钛化合物的还原电位低得多，这可能是5观察到较高活性的原因。
• Analysis of Metallocene−Methylalumoxane Methide Transfer Processes in Solution Using a ¹⁹F NMR Spectroscopic Probe
  作者：Eric J. Hawrelak、Paul A. Deck

  DOI：10.1021/om030171n

  日期：2003.8.1

  The metallocenes (C6F5C5H4)CpZrMe2 (1, Cp = C5H5) and (C6F5C5H4)(2)MMe2 (2a, M = Zr; 2b, M = Hf) were treated with B(C6F5)(3) and, separately, with commercial methylalumoxane (MAO, depleted of excess Me3Al). The ensuing methide transfer reactions were followed by F-19 NMR. Spectra of the "activated" species obtained using MAO and excess B(C6F5)3 were strikingly similar, suggesting that similar "cation-like" species are formed using either organo-Lewis acid, and the MAO-activated species were tentatively formulated as (C6F5C5H4)CpZrMe+ Me[AlMeO](n)(-) and as (C6F5C5H4)(2)MMe+ Me[AlMeO](n)(-) (M = Zr, Hf). The relative amount of L2MMe2 and [L2MMe](+) species observed in solution was measured as a function of [MAO] and as a function of [M] at constant [MAO]. Results are interpreted in terms of a canonical model in which MAO contains relatively few highly active Lewis acidic sites.
• Synthesis of Pentafluorophenyl-Substituted Cyclopentadienes and Their Use as Transition-Metal Ligands
  作者：Paul A. Deck、Woodward F. Jackson、Frank R. Fronczek

  DOI：10.1021/om9608216

  日期：1996.12.10

  The reaction of NaC5H5 (NaCp) and hexafluorobenzene (1:1 ratio) in THF at 25 degrees C for 15 h afforded, after hydrolysis, a mixture of regioisomeric (pentafluorophenyl)cyclopentadienes. This mixture was isolated as a monoisomeric dimer of 1-(pentafluorophenyl)cyclopentadiene. The structure of the dimer was determined crystallographically. Flash vacuum thermolytic cracking of the dimer at 200 degrees C regenerated (pentafluorophenyl)cyclopentadiene as a mixture of regioisomers. In contrast, the reaction of NaCp, NaH, and C6F6 (1:2:5 ratio) in THF at reflux for 3 d affords, after hydrolysis, 1,4-bis(pentafluorophenyl)cyclopentadiene which does not dimerize. Either the mono- or the disubsubstituted diene reacts with NaH in THF;to afford the corresponding stable substituted sodium cyclopentadienides in high yields. Sodium (pentafluorophenyl)cyclopentadienide, (C6F5)C5H4Na, reacted with FeBr2, Re(CO)(5)Br, and ZrCl4(THF)(2), to afford the transition metal complexes (eta(5)-C5H4C6F5)(2)Fe, (eta(5)-C6H4C6F5)Re(CO)(3), and (eta(5)-C5H4C6F5)(2)ZrCl2. Sodium 1,3-bis(pentafluorophenyl)cyclopentadienide reacted with FeBr2 and Re(CO)(5)Br to give the corresponding complexes [eta(5)-1,3-C5H3(C6F5)(2)]Fe-2 and [eta(5)-1,3-C5H3(C6F5)(2)]Re(CO)(3). Infrared spectroscopic analysis of the tricarbonylrhenium(I) complexes and cyclic voltammetric analysis of the substituted ferrocenes quantified the strong electron-withdrawing effects of the pentafluorophenyl substituents.
• Cobalt Complexes Containing Pendant Amines in the Second Coordination Sphere as Electrocatalysts for H₂ Production
  作者：Ming Fang、Eric S. Wiedner、William G. Dougherty、W. Scott Kassel、Tianbiao Liu、Daniel L. DuBois、R. Morris Bullock

  DOI：10.1021/om5004607

  日期：2014.10.27

  A series of heteroleptic 17e cobalt complexes, [CpCoII((P2N2Ph)-N-tBu)](BF4), [(CpCoII)-Co-C6F5((P2N2Ph)-N-tBu)](BF4), and [(CpCoII)-Co-C5F4N((P2N2Ph)-N-tBu)](BF4) (where (P2N2Ph)-N-tBu = 1,5-diphenyl-3,7-di-tert-butyl-1,5-diaza-3,7-diphosphacyclooctane, Cp-C6F5 = C5H4(C6F5), and Cp-C5F4N = C5H4(C5F4N)) were synthesized, and the structures of all three were determined by X-ray crystallography. Electrochemical studies showed that the Co-III/II couple of [CpC5F4NCoII((P2N2Ph)-N-tBu)](+) appears 250 mV positive of the Co-III/II couple of [CpCoII((P2N2Ph)-N-tBu)](+) as a result of the strongly electron withdrawing perfluoropyridyl substituent on the Cp ring. Reduction of these paramagnetic Co-II complexes by KC8 led to the diamagnetic 18e complexes CpCoI((P2N2Ph)-N-tBu), (CpCoI)-Co-C6F5(PtBu2N2Ph), and (CpCoI)-Co-C5F4N(PtBu2N2Ph), which were also characterized by crystallography. Protonation of these neutral Co-I complexes led to the CoIII hydrides [CpCoIII((P2N2Ph)-N-tBu)H](BF4), [(CpCoIII)-Co-C6F5((P2N2Ph)-N-tBu)H](BF4), and [(CpCoIII)-Co-C5F4N(PtBu2N2Ph)H](BF4), and crystal structures of each of these cobalt hydrides were determined. The cobalt complex with the most electron withdrawing Cp ligand, [(CpCoII)-Co-C5F4N((P2N2Ph)-N-tBu)](+), is an electrocatalyst for production of H-2 using [p-MeOC6H4NH3][BF4] (pKa(MeCN) = 11.86), with a turnover frequency of 350 s1 and an overpotential of 0.86 V at E-cat/2. A pKa value of 15.6 was measured in CH3CN for [(CpCoIII)-Co-C5F4N((P2N2Ph)-N-tBu)H], which was used in conjunction with electrochemical measurements to obtain thermodynamic data for cleavage of the CoH bond.