4-methoxyanilinium tetrafluoroborate | 143733-27-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-methoxyanilinium tetrafluoroborate
• 英文别名: 4-Methoxy-Phenylammonium tetrafluoroborate；(4-methoxyphenyl)azanium;tetrafluoroborate
• CAS: 143733-27-1
• 化学式: BF₄*C₇H₉NO*H
• 分子量: 210.967
• InChiKey: SNZSFOYSCMGDKE-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  2.69
• 重原子数：
  14.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  35.25
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4-methoxyanilinium tetrafluoroborate 在 [Cp^C5F4NCo^II(1,5-diphenyl-3,7-di-tert-butyl-1,5-diaza-3,7-diphosphacyclooctane)](BF₄) 、 tert-butylammonium hexafluorophosphate(V) 作用下， 以 乙腈 为溶剂， 生成 氢气
  参考文献：
  名称：

  Cobalt Complexes Containing Pendant Amines in the Second Coordination Sphere as Electrocatalysts for H₂ Production

  摘要：

  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.

  DOI：

  10.1021/om5004607
• 作为产物：
  描述：

  甲氧苯胺 在 tetrafluoroboric acid 作用下， 以 乙醚 为溶剂， 生成 4-methoxyanilinium tetrafluoroborate
  参考文献：
  名称：

  Appel, Aaron M.; Lee, Suh-Jane; Franz, James A., Journal of the American Chemical Society, 2009, vol. 131, p. 5224 - 5232

  摘要：

  DOI：

文献信息

• Reaction Parameters Influencing Cobalt Hydride Formation Kinetics: Implications for Benchmarking H₂-Evolution Catalysts
  作者：Noémie Elgrishi、Daniel A. Kurtz、Jillian L. Dempsey

  DOI：10.1021/jacs.6b10148

  日期：2017.1.11

  for benchmarking hydrogen evolution catalysts has increasingly been recognized. The influence of acid choice on activity is often reduced to the overpotential for catalysis. Through the study of a stable cobalt hydride complex, we demonstrate the influence of acid choice, beyond pKa, on the kinetics of hydride formation. A linear free energy relationship between acid pKa and second-order rate constants

  人们越来越认识到需要对析氢催化剂进行基准测试。酸选择对活性的影响通常被归结为催化过电位。通过对稳定的氢化钴络合物的研究，我们证明了酸选择对氢化物形成动力学的影响，超过 pKa。对于较弱的酸，观察到酸 pKa 和二级速率常数之间的线性自由能关系。然而，对于更强的酸，pKa 的进一步增加与速率常数的增加无关。此外，酸性质子周围的空间体积显示出显着影响速率常数。总之，这些观察结果揭示了决定催化剂性能的复杂因素。
• [Ni(Et₂PCH₂NMeCH₂PEt₂)₂]²⁺ as a Functional Model for Hydrogenases
  作者：Calvin J. Curtis、Alex Miedaner、Rebecca Ciancanelli、William W. Ellis、Bruce C. Noll、M. Rakowski DuBois、Daniel L. DuBois

  DOI：10.1021/ic020610v

  日期：2003.1.1

  ligand in the proton exchange reactions observed for the various Ni complexes containing the PNP ligand. Similarly, structural studies of [Ni(PNBuP)(2)](BF(4))(2) and [Ni(PNP)(dmpm)](BF(4))(2) (where PNBuP is Et(2)PCH(2)N(Bu)CH(2)PEt(2) and dmpm is Me(2)PCH(2)PMe(2)) illustrate the importance of tetrahedral distortions about Ni in determining the hydride acceptor ability of Ni(II) complexes.

  Et（2）PCH（2）N（Me）CH（2）PEt（2）（PNP）与[Ni（CH（3）CN）（6）]（BF（4））（2）的反应结果在[Ni（PNP）（2）]（BF（4））（2）的形成中，它同时具有氢化物和质子受体位点。该络合物是用于将氢氧化为质子的电催化剂，与氢的化学计量反应形成[HNi（PNP）（PNHP）]（BF（4））（2），其中氢化物配体与Ni和质子键合与一个PNP配体的N侧基相连。使用热力学循环，与该反应有关的自由能已计算为-5 kcal / mol。氢化物配体和NH质子相互之间进行快速分子内交换，并与溶液中的质子进行分子间交换。[HNi（PNP）（PNHP）]（BF（4））（2）经历可逆的去质子化反应，在乙腈溶液中形成[HNi（PNP）（2）]（BF（4））（pK（a）= 10.6）。一种方便的合成方法来合成这种氢化物的PF（6）（-）盐包括PNP与Ni（COD）（2）反应形成N
• Direct Determination of Equilibrium Potentials for Hydrogen Oxidation/Production by Open Circuit Potential Measurements in Acetonitrile
  作者：John A. S. Roberts、R. Morris Bullock

  DOI：10.1021/ic302461q

  日期：2013.4.1

  potential in acetonitrile as −0.028(4) V vs the ferrocenium/ferrocene couple. Dimethylformamidium forms homoconjugates and other aggregates with dimethylformamide; open circuit potentials (OCPs) were used to quantify the extent of these reactions. Overpotentials for electrocatalytic hydrogen production and oxidation were determined from open circuit potentials and voltammograms of acidic or basic catalyst solutions

  在1 atm H 2下测量了各种酸及其共轭碱的乙腈溶液的开路电势。所检查的酸为三乙铵，二甲基甲铵，2,6-二氯苯铵，4-氰基苯铵，4-溴苯铵和4-苯胺鎓盐。这些潜力以及p K a酸值，确定乙腈中标准氢电极（SHE）电势的值相对于二茂铁/二茂铁对为-0.028（4）V。二甲基甲ami与二甲基甲酰胺形成均聚物和其他聚集体；开路电势（OCP）用于量化这些反应的程度。由H 2下的酸性或碱性催化剂溶液的开路电势和伏安图确定了电催化制氢和氧化的超电势。对于这些解决方案，OCP值与使用能斯特方程式计算的电势之间的一致性在12 mV以内。使用测得的平衡电位可以直接比较不同介质中的催化体系；它既不需要p K a 值，均轭共轭常数或SHE电位。
• Reactivity of Proton Sources with a Nickel Hydride Complex in Acetonitrile: Implications for the Study of Fuel-Forming Catalysts
  作者：Eric S. Rountree、Jillian L. Dempsey

  DOI：10.1021/acs.inorgchem.6b00885

  日期：2016.5.16

  addition of water, an increase in the observed rate constant was seen, in line with the formation of hydronium. When added to trifluoroacetic acid, water was shown to cause a decrease in the observed rate constant, suggesting that water inhibits acid dimerization. Collectively, these findings highlight that the selection of proton sources for the study of molecular electrocatalysts in acetonitrile must account

  氢化镍配合物[HNi（P 2 Ph N 2 Ph）2 ] +（P 2 Ph N 2 Ph = 1,3,5,7-四苯基-1,5-二氮杂-3,7-二磷环辛烷）的反应性为了评估在乙腈中形成燃料的催化剂时质子源如何影响反应动力学，可以更好地理解质子源如何在乙腈中形成多种酸，从而在乙腈中形成氢。该反应由析氢催化剂[Ni（P 2 Ph N 2 Ph）2 ] 2+的催化循环中的速率确定步骤引发。。就p K a，均共轭，二聚化，杂共轭和聚集（对于水）而言，评估了质子源。还研究了水和共轭碱的作用。速率常数与p K a之间的线性自由能关系被揭示; 对于容易发生共轭作用的酸，其速率常数随其共轭常数的大小而增加，并且对于三氟乙酸和三氯乙酸观察到了二级反应性，表明存在二聚作用。加水后，观察到的速率常数增加，与水合氢盐的形成相一致。当添加到三氟乙酸中时，水显示出所观察到的速率常数降低，表明水抑制了酸二聚作用。总的来说
• Syntheses and Reactions of Iron(II) Complexes Containing Diphosphine Ligands with Pendant Nitrogen Bases
  作者：George M. Jacobsen、R. K. Shoemaker、M. Rakowski DuBois、Daniel L. DuBois

  DOI：10.1021/om700510b

  日期：2007.9.1

  A series of new iron(II)−hydride complexes that contain diphosphine ligands with pendant amine bases of the formula cis-[HFeL(PNP)2]+, where PNP = Et2PCH2NMeCH2PEt2 and L = CH3CN (3), CO (4), P(OEt)3 (5), have been synthesized and characterized. Protonations of the pendant bases in the PNP complexes have been characterized, and for selected complexes, pKa values have been determined. The acidity of

  一系列新的铁（II）-氢化物络合物，其中含有二膦配体和侧基为顺式-[HFeL（PNP）2 ] +的胺侧基，其中PNP = Et 2 PCH 2 NMeCH 2 PEt 2和L = CH 3 CN （3），CO（4），P（OEt）3（5）已合成和表征。已对PNP配合物中悬垂碱基的质子化进行了表征，对于选定的配合物，p K a值已确定。PNHP配体的酸度在很大程度上取决于与其结合的Fe中心的电子性质，范围<7.0至12.7，具体取决于存在的大肠菌素的性质。与先前研究的氢化物配合物[HNi（PNP）2 ] +和反式-[HFe（CH 3 CN）（PNP）（dmpm）] +（其中dmpm为双（二甲基膦基）甲烷）不同，此处报道的新氢化物配合物确实在二膦的质子化碱和氢化物配体之间没有显示出快速的分子内交换。这归因于PNP配体上乙基取代基之间的空间相互作用。