indigo-N,N′-diphenyldiimine | 75863-33-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: indigo-N,N′-diphenyldiimine
• CAS: 75863-33-1
• 化学式: C₂₈H₂₀N₄
• 分子量: 412.494
• InChiKey: OYAAGYAUGARFEA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.69
• 重原子数：
  32.0
• 可旋转键数：
  2.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  48.78
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  indigo-N,N′-diphenyldiimine 在 三乙胺 、 三氟化硼乙醚 作用下， 以 甲苯 为溶剂， 反应 0.66h， 以60.2%的产率得到indigo [diphenylimine]difuoroboron
  参考文献：
  名称：

  Redox-active, near-infrared dyes based on ‘Nindigo’ (indigo-N,N′-diarylimine) boron chelate complexes

  摘要：

  靛蓝-N,N²-二亚胺（"靛蓝"）衍生物与 BF3Â-Et2O 的反应分别产生单-或双-BF2 螯合物 2 或 3。2 和 3 之间的产物分布对辅助碱和溶剂很敏感。虽然双-BF2 复合物 3 可以分离出来，但它们在溶液中会逐渐分解成相应的单-BF2 物种 2；水会加速这一过程。根据对 2 的结构分析，3 的不稳定性被认为是由于环染色效应造成的。对 2 的电化学研究显示了一个准可逆的氧化过程和两个不可逆的还原过程，而 3 的衍生物则具有一个可逆的氧化过程和两个连续的可逆还原过程。2 和 3 的电子光谱分别在 650 纳米和 750 纳米附近含有强烈的（δ§¼ 3 à 104 Mâ1 cmâ1）长波长吸收。这两个系列的化合物在近红外波段都有微弱的辐射。与时间相关的 DFT 计算表明，这些电子跃迁具有 ÏâÏ* 性质。

  DOI：

  10.1039/c2sc21307a
• 作为产物：
  描述：

  苯胺 、 indigo 在 三乙烯二胺 、 四氯化钛 作用下， 以 C₆H₅Br 、 甲苯 为溶剂， 以71%的产率得到indigo-N,N′-diphenyldiimine
  参考文献：
  名称：

  “ Nindigo”：靛蓝二亚胺作为一类新的功能性桥接配体的合成，配位化学和性质。

  摘要：

  靛蓝与苯胺的反应为靛蓝N，N'-二芳基二亚胺（“ Nindigo”）提供了一条简单的途径，N，N'-二芳基二亚胺（“ Nindigo”）是一种新的双核配体，具有两个β-二酮-型金属结合位点。双钯络合物具有令人感兴趣的以配体为中心的特性，例如氧化还原活性和强烈的近红外吸收。

  DOI：

  10.1039/c0cc01736a

文献信息

• NOVEL COMPOUND, NEAR-INFRARED ABSORBENT, AND SYNTHETIC RESIN COMPOSITION CONTAINING SAME
  申请人：Adeka Corporation

  公开号：EP2700644B1

  公开（公告）日：2015-05-20
• Redox-Active Bridging Ligands Based on Indigo Diimine (“Nindigo”) Derivatives
  作者：Graeme Nawn、Kate M. Waldie、Simon R. Oakley、Brendan D. Peters、Derek Mandel、Brian O. Patrick、Robert McDonald、Robin G. Hicks

  DOI：10.1021/ic200388y

  日期：2011.10.17

  Reactions of indigo with a variety of substituted anilines produce the corresponding indigo diimines ("Nindigos") in good yields. Nindigo coordination complexes are subsequently prepared by reactions of the Nindigo ligands with Pd(hfac)(2). In most cases, binudear complexes are obtained in which the deprotonated Nindigo bridges two Pd(hfac) moieties in the expected bis-bidentate binding mode. When the Nindigo possesses bulky substituents on the imine (mesityl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, etc.), mononuclear Pf(hfac) complexes are obtained in which the Nindigo core has isomerized from a trans- to a cis-alkene; in these structures, the palladium is bound to the cis-Nindigo ligand at the two indole nitrogen atoms; the remaining proton is bound between the imine nitrogen atoms. The palladium complexes possess intense electronic absorption bands [near 920 nm for the binuclear complexes and 820 nm for the mononuclear cis-Nindigo complexes; extinction coefficients are (1.0-2.0) x 104 M-1 cm(-1)] that are ligand-centered (pi-pi) transitions. Cyclic voltammetry investigations reveal multiple redox events that are also ligand-centered in origin. All of the palladium complexes can be reversibly oxidized in two sequential one-electron steps; the binuclear complexes are reduced in a two-electron process whose reversibility depends on the Nindigo ligand substituent; the mononuclear palladium species show two one-electron reductions, only the first of which is quasi-reversible.
• A Diruthenium Complex of a “Nindigo” Ligand
  作者：Prasenjit Mondal、Fabian Ehret、Martina Bubrin、Amit Das、Shaikh M. Mobin、Wolfgang Kaim、Goutam Kumar Lahiri

  DOI：10.1021/ic400390b

  日期：2013.8.5

  The compound ((mu-Nindigo)[Ru(acac)(2)](2)} = 1, H-2(Nindigo) = indigo-N,N'-diphenylimine and acac(-) = 2,4-pentanedionate, has been structurally characterized in the rac form, which exhibits two edge-sharing six-membered chelate rings involving ruthenium, and the former beta-diketiminato functions with a twist angle of 33.9 degrees around the central C-C bond. The metric parameters suggest a neutral pi acceptor bridge containing coupled s-trans configurated alpha-diimines, which are coordinated by two ruthenium(II) centers. DFT calculations confirm the experimental structure and oxidation state assignment of the rac form; both diastereoisomers are present in solution according to H-1 NMR spectroscopy. A very intense long-wavelength MLCT absorption at 630 nm (epsilon = 66 800 M-1 cm(-1)) and a weaker near-IR band at 1120 nm (epsilon = 3000 M-1 cm(-1)) are observed for the CH3CN solution. Reversible one-electron reduction and oxidation steps were studied by cyclic voltammetry, differential pulse voltammetry, EPR, and UV-vis-NIR spectroelectrochemistry to exhibit metal-centered oxidation and mixed metal/ligand-centered reduction. These results are supported by TD-DFT calculations of the species rac- or meso-1(n), n = 3+, 2+, +, 0, -, 2-.
• “Nindigo”: synthesis, coordination chemistry, and properties of indigo diimines as a new class of functional bridging ligands
  作者：Simon R. Oakley、Graeme Nawn、Kate M. Waldie、Timothy D. MacInnis、Brian O. Patrick、Robin G. Hicks

  DOI：10.1039/c0cc01736a

  日期：——

  Reactions of indigo with anilines provide a simple route to indigo N,N'-diaryldiimines ("Nindigo"), a new binucleating ligand with two beta-diketiminate-type metal binding sites. Bis-palladium complexes have interesting ligand-centred properties such as redox activity and intense near infrared absorption.

  靛蓝与苯胺的反应为靛蓝N，N'-二芳基二亚胺（“ Nindigo”）提供了一条简单的途径，N，N'-二芳基二亚胺（“ Nindigo”）是一种新的双核配体，具有两个β-二酮-型金属结合位点。双钯络合物具有令人感兴趣的以配体为中心的特性，例如氧化还原活性和强烈的近红外吸收。
• Redox-active, near-infrared dyes based on ‘Nindigo’ (indigo-N,N′-diarylimine) boron chelate complexes
  作者：Graeme Nawn、Simon R. Oakley、Marek B. Majewski、Robert McDonald、Brian O. Patrick、Robin G. Hicks

  DOI：10.1039/c2sc21307a

  日期：——

  Reactions of indigo-N,N′-diarylimine (‘Nindigo’) derivatives with BF3·Et2O give mono- or bis-BF2 chelate complexes 2 or 3 respectively. The product distribution between 2 and 3 is sensitive to the auxiliary base and solvent. Although the bis-BF2 complexes 3 are isolable, they gradually decompose in solution to the corresponding mono-BF2 species 2; this process is accelerated by water. The instability of 3 is believed to be due to ring stain effects based on structural analyses of 2. Electrochemical studies of 2 reveal one quasi-reversible oxidation process and two irreversible reductions, whereas derivatives of 3 possess a reversible oxidation and two sequential reversible reductions. The electronic spectra of 2 and 3 contain intense (ε ∼ 3 × 104 M−1 cm−1) long-wavelength absorptions near 650 nm and 750 nm respectively. Both series of compounds are weakly emissive in the near-infrared. Time-dependent DFT calculations reveal the electronic transitions to be π–π* in nature.

  靛蓝-N,N²-二亚胺（"靛蓝"）衍生物与 BF3Â-Et2O 的反应分别产生单-或双-BF2 螯合物 2 或 3。2 和 3 之间的产物分布对辅助碱和溶剂很敏感。虽然双-BF2 复合物 3 可以分离出来，但它们在溶液中会逐渐分解成相应的单-BF2 物种 2；水会加速这一过程。根据对 2 的结构分析，3 的不稳定性被认为是由于环染色效应造成的。对 2 的电化学研究显示了一个准可逆的氧化过程和两个不可逆的还原过程，而 3 的衍生物则具有一个可逆的氧化过程和两个连续的可逆还原过程。2 和 3 的电子光谱分别在 650 纳米和 750 纳米附近含有强烈的（δ§¼ 3 à 104 Mâ1 cmâ1）长波长吸收。这两个系列的化合物在近红外波段都有微弱的辐射。与时间相关的 DFT 计算表明，这些电子跃迁具有 ÏâÏ* 性质。