sodium (tetrafluoropyridinyl)cyclopentadienide | 1610598-09-8

• 英文名称: sodium (tetrafluoropyridinyl)cyclopentadienide
• 英文别名: NaCp^C5F4N
• CAS: 1610598-09-8
• 化学式: C₁₀H₄F₄NNa
• 分子量: 237.132
• InChiKey: DRQNUUTZYYNWFC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.03
• 重原子数：
  16.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  12.89
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  sodium (tetrafluoropyridinyl)cyclopentadienide 、 (P^EtN^(CH2)4NMe2P^Et)FeCl₂ 以 四氢呋喃 为溶剂， 反应 16.0h， 以89%的产率得到(Cp^C5F4N)Fe(P^EtN^(CH2)4NMe2P^Et)Cl
  参考文献：
  名称：

  外配位球质子中继基及其对铁电催化剂氢氧化的邻近影响

  摘要：

  [（Cp的分子内和分子间的去质子化反应Ç 5 ˚F 4 Ñ）的Fe（P的Et ñ - [R ' P的Et）H] +（P的Et ñ - [R ' P的Et =（ET 2 PCH 2）2 NR'）的复合物氢是氢电催化氧化中的限速过程，可以通过促进去质子化中间体的能量匹配而由外配位球（OCS）中的胺碱介导。一系列具有不同N-取代基的配合物（R'= Me，Et，CH 2 OMe，CH2 N（Ph）Me和（CH 2）n NMe 2；n = 1-4）使用密度泛函理论进行了计算检验，以确定OCS的身份和邻近度对分子内质子化的影响。具有OCS二甲基氨基取代基的配合物最适合能量匹配。仲和OCS氮原子之间的碳原子数决定了氢化铁去质子化后氢键相互作用和环应变的强度。先前报道的[（CP ç 5 ˚F 4 Ñ）的Fe（P的Et ñ - [R ' P的Et）H] +（R'=（CH 2）3 NME 2）电被预测为具有最有利的自由能（Δ

  DOI：

  10.1021/acs.organomet.8b00805
• 作为产物：
  描述：

  五氟吡啶 、 sodium cyclopentadienide 以 四氢呋喃 为溶剂， 反应 1.0h， 以67%的产率得到sodium (tetrafluoropyridinyl)cyclopentadienide
  参考文献：
  名称：

  由多响应微凝胶构建的光学器件

  摘要：

  合成了基于聚（N-异丙基丙烯酰胺）的新型多响应微凝胶，其中含有三苯甲烷亮醇，并用于构建标准品。研究了所得标准具的光学性质，并表征了它们对紫外线和可见光照射的响应，溶液的pH值变化以及存在神经毒药塔邦的模拟物的特征。我们清楚地表明，设备的光学特性极大地取决于这些刺激。这项研究说明了基于微凝胶的标准具结构的多功能性，并展示了此类设备在远程驱动，色彩可调光学，传感和潜在的远程触发药物输送应用中的明确用途。

  DOI：

  10.1002/anie.201402641

文献信息

• Increasing the rate of hydrogen oxidation without increasing the overpotential: a bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay
  作者：Jonathan M. Darmon、Neeraj Kumar、Elliott B. Hulley、Charles J. Weiss、Simone Raugei、R. Morris Bullock、Monte L. Helm

  DOI：10.1039/c5sc00398a

  日期：——

  H₂ oxidation by a molecular electrocatalyst is dramatically improved by controlling proton movement from iron to the outer coordination sphere.

  通过控制质子从铁到外部配位球的移动，分子电催化剂对H2的氧化得到了显著的改善。
• Synthesis and characterization of transition metal complexes bearing tetrafluoro-4-pyridyl substituent on the cyclopentadienyl ring
  作者：Milan Erben、Zdeňka Padělková、Petr Štěpnička、David Veselý、Michal Dušek

  DOI：10.1016/j.ica.2010.06.027

  日期：2010.10

  The reaction of sodium cyclopentadienide (NaCp) with pentafluoropyridine gives Na[4-(C5F4N)C5H4] ((CpNa)-Cp-PyF, 1) contaminated with starting NaCp from which pure 1 could be extracted with Et2O. Hydrolysis of 1 and subsequent crystallization gives pure Diels-Alder dimer 1,4-bis(tetrafluoro-4-pyridyl) tricyclo[5.2.1.0(2,6)]deca-3,8-diene (2). The reactions of 1 with FeCl2, [MnBr(CO)(5)], CoBr2, [Ni(NH3)(6)]Cl-2, [TiCl4(THF)(2)] and [CpTiCl3] cleanly affords the corresponding metallocenes [Fe(Cp-PyF)(2)] (3), [(Cp-PyF)-Mn(CO)(3)] (5), [Co(Cp-PyF)(2)] (6), [Ni(Cp-PyF)(2)] (8), [(Cp-PyF)(2)TiCl2] (9) and [(Cp-PyF)(Cp)TiCl2] (10), respectively. Tetrafluoro-4-pyridyl-substituted ferrocene 3 and [Fe(Cp-PyF)(Cp)] (4) can be alternatively prepared by the reaction of the respective lithioferrocenes with C5F5N in THF. Air-oxidation of complex 6 affords the corresponding cobaltocenium salt [Co(Cp-PyF)(2)]PF6 (7). All prepared compounds were characterized spectroscopically and by elemental analysis. The crystal structures of 3-7 were determined, revealing extensive arene pi center dot center dot center dot pi stacking and C-H center dot center dot center dot F-C contacts. Electrochemical studies supported with the spectroscopic data of the prepared metallocene complexes evidenced strong electron-withdrawing nature of the tetrafluoro-4-pyridyl substituent. (C) 2010 Elsevier B.V. All rights reserved.
• 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.