N,N'-diphenyl-6-aminopentafulvene-1-aldimine

• 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: N,N'-diphenyl-6-aminopentafulvene-1-aldimine
• 英文别名: bis(N,N'-phenyl)-6-aminofulvene-2-aldimine；N,N'-diphenyl-6-aminofulvene-1-aldimine；Ph₂(aminofulvene-formaldiminate)H；Ph₂AFAH；Ph2(6-aminofulvalene-2-aldimine)；Ph2-AFAH；N-[(E)-[2-(phenyliminomethyl)cyclopenta-2,4-dien-1-ylidene]methyl]aniline
• 化学式: C₁₉H₁₆N₂
• 分子量: 272.349
• InChiKey: HLHDYRWKKCBTBG-GDXQVIOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  24.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N,N'-diphenyl-6-aminopentafulvene-1-aldimine 在 氘代甲醇-d 作用下， 生成
  参考文献：
  名称：

  晶体和无定形 N,N'-Diphenyl-6-aminofulvene-1-aldimine 中超快分子内质子互变异构的 NMR 研究：固态、动力学同位素和隧道效应

  摘要：

  使用固态核磁共振光谱，我们在微秒到皮秒的时间尺度上检测并表征了固体 N, N'-diphenyl-6-aminofulvene-1-aldimine (I) 的 NHN 氢键中的超快分子内质子互变异构现象。(15)N 交叉极化魔角自旋 NMR 实验使用 (1)H 去耦对多晶 I-(15)N 2 和相关化合物 N-苯基-N'-(1,3,4-三唑)进行-6-aminofulvene-1-aldimine (II) 提供了关于互变异构过程的热力学信息。我们发现 II 仅形成一个互变异构体，但 I 的两个互变异构体的气相简并性被固态相互作用解除。速率常数，包括 H/D 动力学同位素效应 (KIE)，通过测量和分析 I- (15)N 2、I- (15)N 2- d 10 和 I 的纵向 (15)N 和 (2)H 弛豫时间，获得微秒到皮秒时间尺度上的- (15)N 2- d 1 在很宽的温度范围内。除了微晶改性外，还发现并研究了

  DOI：

  10.1021/ja801506n
• 作为产物：
  描述：

  6-(二甲氨基)富烯 在 草酰氯 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 34.0h， 生成 N,N'-diphenyl-6-aminopentafulvene-1-aldimine
  参考文献：
  名称：

  Synthesis and Structure of 6-Aminofulvene-2-aldiminate Complexes

  摘要：

  We report here a synthetic route to bis(N,N'-aryl)-6-aminofulvene-2-aldimine (AFA) ligand systems, specifically Ph-2-AFAH and Dip(2)-AFAH. The synthesis and structural characterization of a series of Cu(I) complexes [(Ph-2-AFA)-Cu(CNPh)(2)] (2), [(Ph-2-AFA)Cu(CN'Pr)] (3), and [(Dip(2)-AFA)Cu(CN'Pr)] (4), from the reaction of the corresponding lithiated AFA systems with Cu-Cl derivatives are reported; notably in the case of [(Ph-2-AFA)Cu(CNPh)(2)] studies have revealed the existence of two structural isomers (2a and 2b), both of which can be isolated and structurally characterized. Density functional theory (DFT) calculations suggest that the two crystal forms are comparatively close in energy, and geometry optimization reveals a convergence of these two forms to a geometry that more closely resembles the solid-state structure of isomer 2b, having a CH center dot center dot center dot pi interaction. The reactions of the AFA compounds Ph-2-AFAH and Dip(2)-AFAH with ZnMe2 and AlMe3 have also been investigated, and the results of these reactions are described here.

  DOI：

  10.1021/ic101524b

文献信息

• Metalloligands containing aminofulvene-aldiminate (AFA) ligands and their bimetallic complexes
  作者：Philip J. Bailey、Mahmudur Rahman、Simon Parsons、Muhammad R. Azhar、Fraser J. White

  DOI：10.1039/c2dt32804f

  日期：——

  A simple and convenient route to η5-coordinated Ru and Rh aminofulvene-aldiminate (AFA) complexes is described. The metalloligands [Cp*Ruη5-(Ph2AFAH)}][BF4] (3), [Cp*Ruη5-(benzyl2AFAH)}][OTf] (7), [Cp*Rhη5-(Cy2AFA)H}][BF4]2 (8) and [Cp*Rhη5-(Cy2AFA)}][BF4] (9) have been synthesised and characterised. The basicity of 9 has been found to be significantly less than its neutral analogue and thus eliminates the need for a deprotonation step to ligate to a second metal in the κ2-N,N′-coordination mode. The reaction of 9 with a palladium precursor provides a mixed-metal complex [Cp*Rh(η5/κ2-Cy2AFA)PdCl2][BF4] (12). Cyclic voltammetry studies of the Ph2AFAH ligand shows an irreversible one electron oxidation peak at +1.0 V (vs. Fc/Fc+). Complex 3 shows an irreversible oxidation at +1.5 V and a reduction peak at −1.0 V. The oxidation of 3 occurs on the AFA ligand backbone whereas the structurally analogous neutral 1,2-bis(imidoyl)pentamethyl-ruthenocene shows reversible oxidation at the Ru center.

  本文描述了一种简单方便的方法来制备 η5 配位的 Ru 和 Rh 氨基乙醛酸盐 (AFA) 复合物。合成并表征了金属配体 [Cp*Ruη5-(Ph2AFAH)}][BF4] (3)、[Cp*Ruη5-(苄基 2AFAH)}][OTf](7)、[Cp*Rhη5-(Cy2AFA)H}][BF4]2 (8) 和 [Cp*Rhη5-(Cy2AFA)}][BF4] (9)。研究发现，9 的碱性明显低于其中性类似物，因此无需去质子化步骤就能以κ2-N,N′配位模式与第二种金属连接。9 与钯前体反应生成了一种混合金属复合物 [Cp*Rh(η5/κ2-Cy2AFA)PdCl2][BF4]（12）。Ph2AFAH 配体的循环伏安研究显示，在 +1.0 V 处有一个不可逆的单电子氧化峰（对 Fc/Fc+）。配合物 3 在 +1.5 V 处出现不可逆氧化，在 -1.0 V 处出现还原峰。络合物 3 的氧化发生在 AFA 配体骨架上，而结构类似的中性 1,2-双（亚胺酰）五甲基钌则显示出 Ru 中心的可逆氧化。
• Palladium complexes of 6-aminofulvene-2-aldiminate (AFA) ligands
  作者：Philip J. Bailey、Anna Collins、Peter Haack、Simon Parsons、Mahmudur Rahman、Damian Smith、Fraser J. White

  DOI：10.1039/b914707a

  日期：——

  (4) has been synthesised and characterised. The synthesis and characterisation of two zwitterionic Pd(II) complexes [(Ph2AFA)Pd(Me)DMAP] (1) and [(Ph2AFA)Pd(N,N-dimethylbenzylamine-2-C,N)] (2) are reported. Activation of 1 and 2 for ethene polymerisation with Lewis acids such as BF3 and B(C6F5)3 were not successful. Attempted synthesis of halide-bridged dimers of the form [(Ph2AFA)Pd(μ-X)]2 resulted in

  双（Ñ，Ñ '-2,6-二异丙基苯基）-6- aminofulvene -2-醛亚胺（4）已经被合成和表征。两种两性离子的合成与表征钯（II） 配合物[（Ph 2 AFA）Pd（Me）DMAP]（1）和[（Ph 2 AFA）Pd（N，N-二甲基苄胺-2-C，N）]（2）报道。的活化1和2为乙烯用路易斯酸如BF 3和B（C 6 F 5）3的聚合反应不成功。尝试合成卤化物桥联的二聚体形式[（Ph 2 AFA）Pd（μ-X）] 2 导致形成双螯合物[（Cy 2 AFA）2 Pd]（3）和[（t Bu 2 AFA）2 Pd]（5）。
• Ambidentate Character of the 6-Aminofulvene-2-aldiminate Ligand Containing Both Diimine and Cyclopentadienyl Donors
  作者：Philip J. Bailey、Michele Melchionna、Simon Parsons

  DOI：10.1021/om060808d

  日期：2007.1.1

  ate (AFA) ligand contains both cyclopentadienyl and diimine donors. The ligand preferentially coordinates to transition metals via the nitrogen atoms; however once these are occupied, the cyclopentadienyl ring may be coordinated to a Cp*Ru+ unit, providing bi- and trimetallic species. In the tetrahedral [Zn(Ph2AFA)2] (2) the metal is located approximately in the planes of the two ligands; however in

  6-氨基富勒烯-2-醛（AFA）配体同时包含环戊二烯基和二亚胺供体。配体优先通过氮原子配位到过渡金属上。然而，一旦这些被占据，环戊二烯基环可被配位至Cp * Ru +单元，从而提供双金属和三金属物种。在四面体[Zn（Ph 2 AFA）2 ]（2）中，金属大约位于两个配体的平面中；但是在正方形[Pd（Ph 2 AFA）2 ]（1）配位会严重变形，并且金属位于两个配体平面的近1.3Å处。出现这种情况是为了避免配体苯基取代基的空间相互作用。的治疗2与混合[Cp *茹（NCMe）3 ] [BF 4 ]给出的[Cp *茹（η 5 -Ph 2 AFA）]（3），提供了一个AFA的环戊二烯基配体配位，其中所述的第一个例子氮供体是空的，并且据认为是由于中间混合的Zn / Ru物种碎裂而形成的。X射线结构图3为Ru中心与一个环外碳原子之间的相互作用提供了一些证据，从而表明了该配合物中配体的富烯形式。用[Cp
• Synthesis and Structure of 6-Aminofulvene-2-aldiminate Complexes
  作者：Alexander M. Willcocks、Alexander Gilbank、Stephen P. Richards、Simon K. Brayshaw、Andrew J. Kingsley、Raj Odedra、Andrew L. Johnson

  DOI：10.1021/ic101524b

  日期：2011.2.7

  We report here a synthetic route to bis(N,N'-aryl)-6-aminofulvene-2-aldimine (AFA) ligand systems, specifically Ph-2-AFAH and Dip(2)-AFAH. The synthesis and structural characterization of a series of Cu(I) complexes [(Ph-2-AFA)-Cu(CNPh)(2)] (2), [(Ph-2-AFA)Cu(CN'Pr)] (3), and [(Dip(2)-AFA)Cu(CN'Pr)] (4), from the reaction of the corresponding lithiated AFA systems with Cu-Cl derivatives are reported; notably in the case of [(Ph-2-AFA)Cu(CNPh)(2)] studies have revealed the existence of two structural isomers (2a and 2b), both of which can be isolated and structurally characterized. Density functional theory (DFT) calculations suggest that the two crystal forms are comparatively close in energy, and geometry optimization reveals a convergence of these two forms to a geometry that more closely resembles the solid-state structure of isomer 2b, having a CH center dot center dot center dot pi interaction. The reactions of the AFA compounds Ph-2-AFAH and Dip(2)-AFAH with ZnMe2 and AlMe3 have also been investigated, and the results of these reactions are described here.
• NMR Studies of Ultrafast Intramolecular Proton Tautomerism in Crystalline and Amorphous <i>N</i>,<i>N</i>′-Diphenyl-6-aminofulvene-1-aldimine: Solid-State, Kinetic Isotope, and Tunneling Effects
  作者：Juan Miguel Lopez del Amo、Uwe Langer、Verónica Torres、Gerd Buntkowsky、Hans-Martin Vieth、Marta Pérez-Torralba、Dionísia Sanz、Rosa María Claramunt、José Elguero、Hans-Heinrich Limbach

  DOI：10.1021/ja801506n

  日期：2008.7.1

  ( II) provided information about the thermodynamics of the tautomeric processes. We found that II forms only a single tautomer but that the gas-phase degeneracy of the two tautomers of I is lifted by solid-state interactions. Rate constants, including H/D kinetic isotope effects (KIEs), on the microsecond-to-picosecond time scale were obtained by measuring and analyzing the longitudinal (15)N and

  使用固态核磁共振光谱，我们在微秒到皮秒的时间尺度上检测并表征了固体 N, N'-diphenyl-6-aminofulvene-1-aldimine (I) 的 NHN 氢键中的超快分子内质子互变异构现象。(15)N 交叉极化魔角自旋 NMR 实验使用 (1)H 去耦对多晶 I-(15)N 2 和相关化合物 N-苯基-N'-(1,3,4-三唑)进行-6-aminofulvene-1-aldimine (II) 提供了关于互变异构过程的热力学信息。我们发现 II 仅形成一个互变异构体，但 I 的两个互变异构体的气相简并性被固态相互作用解除。速率常数，包括 H/D 动力学同位素效应 (KIE)，通过测量和分析 I- (15)N 2、I- (15)N 2- d 10 和 I 的纵向 (15)N 和 (2)H 弛豫时间，获得微秒到皮秒时间尺度上的- (15)N 2- d 1 在很宽的温度范围内。除了微晶改性外，还发现并研究了