1-(2-(diphenylphosphino)phenyl)-2,5-dimethyl-1H-pyrrole | 1616734-31-6

• 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: 1-(2-(diphenylphosphino)phenyl)-2,5-dimethyl-1H-pyrrole
• 英文别名: [2-(2,5-Dimethylpyrrol-1-yl)phenyl]-diphenylphosphane；[2-(2,5-dimethylpyrrol-1-yl)phenyl]-diphenylphosphane
• CAS: 1616734-31-6
• 化学式: C₂₄H₂₂NP
• 分子量: 355.419
• InChiKey: XDNABHRSGFHWSD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  4.9
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  双(乙腈)氯化钯(II) 、 1-(2-(diphenylphosphino)phenyl)-2,5-dimethyl-1H-pyrrole 以 二氯甲烷 为溶剂， 反应 0.33h， 以95%的产率得到
  参考文献：
  名称：

  A “Hemilabile” Palladium–Carbon Bond: Characterization and Its Implication in Catalysis

  摘要：

  An unusual palladium carbon bond was identified in the crystal structure of a Pd(II) complex (VI) derived from 1-(2-diphenylphosphinophenyl)-2,5-dimethyl-1H-pyrrole (LA). Theoretical calculations indicate that the Pd C bond is covalent in nature. The complex exhibits fluxional behavior in solution at ambient temperature the Pd binds alternately to C2 and CS of pyrrole, generating equivalent, enantiomeric structures. Theory predicts that the transition state of this interconversion probably occurs through an unsaturated 14e complex, where the ligand binds the metal in a monodentate fashion. Comparison with related structures reported earlier has been made, and the possible implication of such unusual bonding in the context of catalysis of coupling reactions is discussed.

  DOI：

  10.1021/om5005435
• 作为产物：
  描述：

  2-溴苯胺 在 正丁基锂 、 硫酸 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 25.0h， 生成 1-(2-(diphenylphosphino)phenyl)-2,5-dimethyl-1H-pyrrole
  参考文献：
  名称：

  Fluxional 氯吡咯-Pd(II) 络合物到阳离子 η2-吡咯-Pd(II) 络合物：结构导向键合模式的微妙之处

  摘要：

  如果 η 1 -碳通过“半稳定的”钯-碳 η 1 -吡咯连接被 N 原子取代，则η 1 -芳族碳环连接的 Pd( II ) 配合物的流动性得以保留。在此，我们报告并表征了一种四配位的中性氯吡咯-Pd( II )-π-烯丙基配合物，其在室温下表现出动态行为。AgSbF 6提取氯后，形成阳离子钯配合物，其中金属的配位球通过吡咯环的一个 C C 双键的配位完成。这种阳离子 η 2 -吡咯连接的 Pd( II)-π-烯丙基配合物的晶体学特征。这些同构复合物中吡咯的配位模式随着碳配体（σ 或 π）的变化而微妙地变化。

  DOI：

  10.1039/d1nj00866h

文献信息

• A “Hemilabile” Palladium–Carbon Bond: Characterization and Its Implication in Catalysis
  作者：Debajyoti Saha、Ravi Verma、Devesh Kumar、Shubhrodeep Pathak、Sourav Bhunya、Amitabha Sarkar

  DOI：10.1021/om5005435

  日期：2014.7.14

  An unusual palladium carbon bond was identified in the crystal structure of a Pd(II) complex (VI) derived from 1-(2-diphenylphosphinophenyl)-2,5-dimethyl-1H-pyrrole (LA). Theoretical calculations indicate that the Pd C bond is covalent in nature. The complex exhibits fluxional behavior in solution at ambient temperature the Pd binds alternately to C2 and CS of pyrrole, generating equivalent, enantiomeric structures. Theory predicts that the transition state of this interconversion probably occurs through an unsaturated 14e complex, where the ligand binds the metal in a monodentate fashion. Comparison with related structures reported earlier has been made, and the possible implication of such unusual bonding in the context of catalysis of coupling reactions is discussed.
• Steric vis-à-vis electronic influence of phosphines on biaryl motif: Ligand design for coupling reactions with Chloroarenes
  作者：Debajyoti Saha、Raju Ghosh、Ranjan Dutta、Achintya Kumar Mandal、Amitabha Sarkar

  DOI：10.1016/j.jorganchem.2014.11.008

  日期：2015.1

  In order to assess relative contribution of steric factors and electron-richness of phosphine ligands on biaryl-type scaffolds, a set of 1-aryl-pyrazole/pyrrole derived ligands L1-L6 featuring either aryldicyclohexylphosphino or aryldiphenylphosphino donor group was synthesized. A bidentate coordination mode of ligands L1 or L2 was evident from a representative crystal structure that implied a possible hemilabile participation to facilitate catalytic steps. With N-arylpyrroles (L3-L5), where the second nitrogen donor on the heterocycle is absent, coupling reactions of unactivated chloroarenes still proceeded with comparable efficiency. Thus, suitably endowed triarylphosphines were found to be as efficient as more expensive aryldialkylphosphine analogs in reactions with chloroarenes, extending the scope of ligand design. (C) 2014 Elsevier B.V. All rights reserved.
• Fluxional chloro-pyrrole–Pd(<scp>ii</scp>) complex to cationic η²-pyrrole–Pd(<scp>ii</scp>) complex: subtlety in structure-directed bonding mode
  作者：Debajyoti Saha、Nayim Sepay

  DOI：10.1039/d1nj00866h

  日期：——

  carbocyclic-ligated Pd(II) complexes is retained if the η1-carbon is replaced with an N atom through “hemilabile” palladium–carbon η1-pyrrole ligation. Herein, we report and characterize a tetra-coordinated neutral chloro-pyrrole–Pd(II)-π-allyl complex, which shows dynamic behavior at room temperature. Upon chlorine abstraction by AgSbF6, a cationic palladium complex is formed, where the coordination sphere of the

  如果 η 1 -碳通过“半稳定的”钯-碳 η 1 -吡咯连接被 N 原子取代，则η 1 -芳族碳环连接的 Pd( II ) 配合物的流动性得以保留。在此，我们报告并表征了一种四配位的中性氯吡咯-Pd( II )-π-烯丙基配合物，其在室温下表现出动态行为。AgSbF 6提取氯后，形成阳离子钯配合物，其中金属的配位球通过吡咯环的一个 C C 双键的配位完成。这种阳离子 η 2 -吡咯连接的 Pd( II)-π-烯丙基配合物的晶体学特征。这些同构复合物中吡咯的配位模式随着碳配体（σ 或 π）的变化而微妙地变化。