2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanyl-4-methylphenyl]-N,4-dimethylaniline | 691894-26-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanyl-4-methylphenyl]-N,4-dimethylaniline
• CAS: 691894-26-5
• 化学式: C₂₇H₄₃NP₂
• 分子量: 443.593
• InChiKey: QJTPYCMZDNRHPG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanyl-4-methylphenyl]-N,4-dimethylaniline 以 四氢呋喃 、 氘代苯 、 异丙醇 为溶剂， 生成
  参考文献：
  名称：

  N-C和N-H键与零价镍，钯和铂的氧化加成

  摘要：

  基于双（邻膦基芳基）胺亚结构的螯合型PNP配体的反应，其中包含NH（PN（H）P，1）或N-Me（PN（Me）P，2）中心部分与第10组配合物已被探索。与MCl 2（MCl 2 = NiCl 2，（COD）PdCl 2，（COD）PtCl 2，COD = 1,5-环辛二烯）的反应很容易进行，会丢失HCl或MeCl并形成（PNP）MCl（7）其中PNP是阴离子，子午酰胺基-PNP配体。（PNP）MeCl与MeMgCl烷基化得到（PNP）MMe（9），（PNP）MCl与过量的NaBH 4反应提供（PNP）MH（8）。（PNP）MH（8）化合物与CDCl 3反应以再生（PNP）MCl（7）。与M = Ni或Pd相比，M = Pt的转换7 → 8 → 7 → 9变慢。确定（PNP）PdH（8b-Pd）和（PNP）PdMe（9b-Pd）的固态结构。在任何一种结构中，Pd的周围环境都是近似正方形的平面

  DOI：

  10.1021/om0493513
• 作为产物：
  描述：

  bis(2-bromo-4-methylphenyl)amine 在 正丁基锂 、 六甲基二硅氮烷 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 4.25h， 生成 2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanyl-4-methylphenyl]-N,4-dimethylaniline
  参考文献：
  名称：

  Facile Oxidative Addition of N−C and N−H Bonds to Monovalent Rhodium and Iridium

  摘要：

  An investigation of room-temperature oxidative addition of N-C and N-H bonds to RhI and IrI in solution and in the solid state is presented. The rigid, product-adapted framework of the pincer bis(ortho-phosphinoaryl)amine (PNP) ligand may contribute to the ease of the N-C and N-H cleavage. The migration of Me from N of the coordinated amine moiety to Rh proceeds with near-zero entropy of activation in solution. In the solid state, this transformation is a crystal-to-crystal reaction, transforming only one of the two independent molecules of (PN(Me)P)RhCl into (PNP)Rh(Me)Cl.

  DOI：

  10.1021/ja049659l

文献信息

• Competitive Activation of N−C and C−H Bonds of the PNP Framework by Monovalent Rhodium and Iridium
  作者：Wei Weng、Chengyun Guo、Claudia Moura、Lin Yang、Bruce M. Foxman、Oleg V. Ozerov

  DOI：10.1021/om050346o

  日期：2005.7.1

  This work describes how reactions of oxidative addition of N−C and C−H bonds are in competition in the PNP-ligated Rh and Ir complexes. Iridium appears to have a higher preference than Rh for the C−H activation over the N−C activation, and the Ir C−H activated complexes are more kinetically stable than their Rh analogues. A new generation of a diarylamido-based PNP pincer is presented, a “tied” PNP

  这项工作描述了N-C和C-H键的氧化加成反应在PNP连接的Rh和Ir络合物中如何竞争。铱似乎比Rh具有更高的优先权，其CH活化作用优于Nc活化作用，并且Ir CH活化的络合物比Rh的类似物在动力学上更稳定。提出了新一代的基于二芳基酰胺的PNP钳，一种基于亚氨基二苄基亚结构的“并列” PNP配体1c。该配体被更明确地预定为以子午线，阴离子PNP方式与金属中心结合。结果，它的N-C裂解反应（导致阴离子PNP的络合物）比“未结合”的配体1a，b更快。结构证据表明，当受主原子构象的影响时，在供体原子上带有相同的取代基时，“并列”阴离子PNP钳形配体比“未并列”配体更大。“并列”的钳形配体还允许观察中心N-CH 3基团的CH键的激活产物，而“未并列”的配体未检测到。与“未结合”配体的NC氧化加成反应以固态以及在溶液中进行。据报道，固态N-C氧化加成反应比溶液反应具有更高的选择性，结果显着。通过同位素标记（2
• N−C Cleavage in Pincer PNP Complexes of Palladium
  作者：Lei Fan、Lin Yang、Chengyun Guo、Bruce M. Foxman、Oleg V. Ozerov

  DOI：10.1021/om049651k

  日期：2004.9.1

  Several new N-methylated diarylamine-based PNP pincer ligands have been prepared. The synthesis of these ligands is modular and allows incorporation of a variety of substituents that change the solubility and the stereoelectronic properties of the ligand as well as allow for the introduction of a sensitive F-19 NMR spectroscopic probe. The reactions of PN(Me)P ligands with PdX2 (X = Cl, OAc) initially proceed with formation of an adduct, (PN(Me)P)PdX2, that may exist in either the neutral or the ionic forms. These adducts are unreactive in the case of PPh2-bearing ligands, but with the more donating PPr2i-bearing ligands, the adduct evolves into square planar (PNP)PdX with irreversible loss of MeX. Thus, the feasibility of cleavage of an unstrained N-C bond by Pd-II is demonstrated. The N-C cleavage is accelerated by decreasing the solvent polarity. The mechanism may involve either N-C oxidative addition or a nucleophilic attack (external or internal) of X- on the Me group of the N-bound PN(Me)P ligand.
• ORGANOMETALLIC COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE INCLUDING THE SAME
  申请人：SAMSUNG DISPLAY CO., LTD.

  公开号：US20160359126A1

  公开（公告）日：2016-12-08

  An organometallic compound represented by ML 1 L 2 and an organic light-emitting device including the same, wherein M may be selected from copper (Cu), cobalt (Co), and nickel (Ni), L 1 may be selected from ligands represented by Formula 2, and L 2 may be a monovalent organic ligand: When the organometallic compound represented by ML 1 L 2 is used as a dopant in the emission layer of an organic light-emitting device, the organic light-emitting device may have low driving voltage and high quantum efficiency.