2,5-bis[[bis(1-methylethyl)phosphino]methyl]-1H-pyrrole

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 2,5-bis[[bis(1-methylethyl)phosphino]methyl]-1H-pyrrole
• 英文别名: (2,5-Bis[[bis(1-methylethyl)phosphino]methyl]-1h-pyrrole)；[5-[di(propan-2-yl)phosphanylmethyl]-1H-pyrrol-2-yl]methyl-di(propan-2-yl)phosphane
• 化学式: C₁₈H₃₅NP₂
• 分子量: 327.43
• InChiKey: DKYJJIVHONVCHO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  15.8
• 氢给体数：
  1
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2,5-bis[[bis(1-methylethyl)phosphino]methyl]-1H-pyrrole 在 lithium hexamethyldisilazane 作用下， 以 甲苯 为溶剂， 反应 38.0h， 生成
  参考文献：
  名称：

  Synthesis and Application of Pyrrole-Based PNP–Ir Complexes to Catalytic Transfer Dehydrogenation of Cyclooctane

  摘要：

  A series of Bu-t- and Pr-i-substituted PNP pincer Ir and Rh complexes with pyrrole-based core were synthesized and characterized. The structures of the obtained complexes were varied depending on the size of alkyl substituents and ligands other than PNP ligand. All of them exhibit low activity toward transfer dehydrogenation of cyclooctane.

  DOI：

  10.1021/acs.organomet.8b00072
• 作为产物：
  描述：

  二异丙基磷化氢 、 2,5-bis-(dimethylaminomethyl)pyrrole 反应 48.0h， 以78.3%的产率得到2,5-bis[[bis(1-methylethyl)phosphino]methyl]-1H-pyrrole
  参考文献：
  名称：

  Ag(I) and Tl(I) Precursors as Transfer Agents of a Pyrrole-Based Pincer Ligand to Late Transition Metals

  摘要：

  A PNP ligand, (PNP)-P-pyr (((PNP)-P-pyr)H = 2,5-bis((di-iso-propylphosphino)methyl)pyrrole), which employs a pyrrole unit as a central anionic nitrogen donor, was designed. The corresponding group 10 metal chlorides as well as iridium and ruthenium compounds were isolated. In order to conduct this work, [((PNP)-P-pyr)Tl] and [((PNP)-P-pyr)Ag](2) were synthesized and characterized. The thallium and silver species were paramount in the formation of the iridium and ruthenium complexes, which could not be isolated using ((PNP)-P-pyr)H or the corresponding lithium pyrrolide salt. Interestingly, the solid state molecular structure of [((PNP)-P-pyr)Tl] indicates that the metal center engages in an eta(2) intermolecular interaction with the backbone of a neighboring pyrrole molecule instead of the expected bonding to the phosphine arms.

  DOI：

  10.1021/ic501600s

文献信息

• Homolytic H₂ cleavage by a mercury-bridged Ni(<scp>i</scp>) pincer complex [{(PNP)Ni}₂{μ-Hg}]
  作者：Markus Kreye、Matthias Freytag、Peter G. Jones、Paul G. Williard、Wesley H. Bernskoetter、Marc D. Walter

  DOI：10.1039/c4cc09743b

  日期：——

  The Hg-bridged (PNP)Ni-complex acts as a synthon for Ni(i) and homolytically cleaves H₂ to yield [(PNP)NiH].

  Hg桥联的（PNP）镍配合物作为Ni（i）的合成试剂，并通过自由基裂解H2产生[(PNP)NiH]。
• Pyrrole-Based Ti(III) and Ti(IV) PNP Pincer Complexes: Insertion of Ketones into the Ti(IV)-Phosphorus Bond
  作者：Gerald Tomsu、Berthold Stöger、Karl Kirchner

  DOI：10.1021/acs.organomet.3c00327

  日期：2023.10.23

  reactivity of pyrrole-based Ti(III) and Ti(IV) PNP pincer complexes are described. [P(NH)P-iPr] (1) reacts with [TiCl4(THF)2] at room temperature in the presence of NEt3 to afford the Ti(IV) complex [Ti(PNPiPr)(Cl)3]. This complex reacts with acetone and cyclopentanone to give complexes [Ti(PNOacet-iPr)(Cl)3] and [Ti(PNOcyclo-iPr)(Cl)3], respectively. Insertion of the ketone into the Ti(IV)-P bond took place

  描述了基于吡咯的 Ti(III) 和 Ti(IV) PNP 钳配合物的合成、表征和反应性。[P(NH)P- i Pr] ( 1 ) 在室温下、NEt 3存在下与 [TiCl 4 (THF) 2 ] 反应生成 Ti(IV) 络合物 [Ti(PNP i Pr )(Cl) 3 ]。该络合物与丙酮和环戊酮反应，分别生成络合物[Ti(PNO acet - i Pr)(Cl) 3 ]和[Ti(PNO cyclo - i Pr)(Cl) 3 ]。酮插入 Ti(IV)-P 键，形成新的三齿 PNO 配体。用[P(NH)P -i Pr]的锂盐处理[TiCl 3 (THF) 3 ] ，后处理得到配合物[Ti(PNP- i Pr)(Cl) 2 (THF)]，一种顺磁性物质。 μ eff值为 1.8(1) μ B的配合物，对应于一个不成对电子和+III 的形式氧化态。该化合物不与酮反应。提出了基于 DFT 计算的
• Synthesis and characterization of pyrrole-based group 4 PNP pincer complexes
  作者：Gerald Tomsu、Berthold Stöger、Karl Kirchner

  DOI：10.1007/s00706-024-03171-x

  日期：2024.2

  The synthesis, characterization, and reactivity of several group 4 metal complexes featuring a central anionic pyrrole moiety connected via CH2 linkers to two phosphine donors is described. Treatment of [P(NH)P-iPr] with [MCl4(THF)2] (M = Zr, Hf) in the presence of base yields the dimeric complexes [M(PNPiPr)(μ-Cl)(Cl)2]2 featuring two bridging chloride ligands. These complexes react with sodium cyclopentadienyl

  描述了几种第 4 族金属络合物的合成、表征和反应性，这些络合物具有通过 CH 2连接体与两个膦供体连接的中心阴离子吡咯部分。在碱存在下用 [MCl 4 (THF) 2 ] (M = Zr, Hf) 处理 [P(NH)P- i Pr] 产生二聚复合物 [M(PNP i Pr )(μ-Cl)( Cl) 2 ] 2具有两个桥连氯化物配体。这些络合物与环戊二烯基钠和SiMe 3 I反应，分别得到单核络合物[M(PNP i Pr )(η 5 -Cp)(Cl) 2 ]和[M(PNP i Pr )(I) 3 ]。后者与MeMgBr反应形成三烷基配合物[M(PNP i Pr )(Me) 3 ]。用[P(NH)P- i Pr]处理[Ti(NMe 2 ) 4 ]后，获得具有通式[Ti(PNP i Pr )(NMe 2 ) 3 ]的络合物。 DFT 计算表明，最稳定的物质是 [Ti(κ 1 N - PNP i Pr