[1-di(propan-2-yl)phosphanyl-5,6-dihydrobenzo[b][1]benzazepin-11-id-10-yl]-di(propan-2-yl)phosphane;palladium(2+);chloride | 861250-03-5

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [1-di(propan-2-yl)phosphanyl-5,6-dihydrobenzo[b][1]benzazepin-11-id-10-yl]-di(propan-2-yl)phosphane;palladium(2+);chloride
• CAS: 861250-03-5
• 化学式: C₂₆H₃₈ClNP₂Pd
• 分子量: 568.415
• InChiKey: QGVQIEWAKVKLIY-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.97
• 重原子数：
  31
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [1-di(propan-2-yl)phosphanyl-5,6-dihydrobenzo[b][1]benzazepin-11-id-10-yl]-di(propan-2-yl)phosphane;palladium(2+);chloride 、 diethylzinc 以 甲苯 为溶剂， 以62%的产率得到
  参考文献：
  名称：

  Understanding Pd–Pd Bond Length Variation in (PNP)Pd–Pd(PNP) Dimers

  摘要：

  Analysis of the structures of three (PNP)Pd-Pd(PNP) dimers [where PNP stands for anionic diarylamido/bis(phosphine) pincer ligands] has been carried out with the help of single-crystal X-ray diffractometry and density functional theory (DFT) calculations on isolated molecules. The three dimers under study possess analogous ancillary ligands; two of them differ only by an F versus Me substituent in a remote (five bonds away from Pd) position of the pincer ligand. Despite these close similarities, X-ray structural determinations revealed two distinct structural motifs: a highly symmetric molecule with a long Pd-Pd bond or a highly distorted molecule with Pd-Pd bonds ca. 0.14 angstrom shorter. DFT calculations on a series of (PNP)Pd-Pd(PNP) dimers (as molecules in the gas phase) confirmed the existence of these distinct minima for dimers carrying large isopropyl substituents on the P-donor atoms (as in the experimental structure). These minima are nearly isoergic conformers. Evidently, the electronically preferred symmetric structure for the dimer (with a square-planar environment about Pd and a linear N-Pd-Pd-N vector) is not sterically possible with the preferred Pd-Pd distance. Thus, the minima correspond to either a symmetric structure with a long Pd-Pd bond distance or a structure with a short Pd-Pd distance but with substantial distortions in the Pd coordination environment to alleviate steric conflict. This notion is supported by finding only a single minimum (symmetric and with short Pd-Pd bonds) for each of the dimers carrying smaller substituents (H or Me) on the P atoms, regardless of the remote substitution.

  DOI：

  10.1021/ic301629m
• 作为产物：
  描述：

  dichloro(cycloocta-1,5-diene)palladium (II) 、 [1-Di(propan-2-yl)phosphanyl-11-methyl-5,6-dihydrobenzo[b][1]benzazepin-10-yl]-di(propan-2-yl)phosphane 以 甲苯 为溶剂， 以80%的产率得到[1-di(propan-2-yl)phosphanyl-5,6-dihydrobenzo[b][1]benzazepin-11-id-10-yl]-di(propan-2-yl)phosphane;palladium(2+);chloride
  参考文献：
  名称：

  单价铑和铱对PNP框架的N-C和C-H键的竞争性激活

  摘要：

  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

  DOI：

  10.1021/om050346o