cis-chloro(o-tolyl)(1,3-bis(diphenylphosphino)propane)nickel(II) | 1187370-29-1

• 英文名称: cis-chloro(o-tolyl)(1,3-bis(diphenylphosphino)propane)nickel(II)
• 英文别名: (o-tolyl)NiCl(dppp)；(o-tolyl)NiCl(1,3-bis(diphenylphosphino)propane)
• CAS: 1187370-29-1
• 化学式: C₃₄H₃₃ClNiP₂
• 分子量: 597.727
• InChiKey: REVLMXAHVNGRLH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  1,3-bis[(diphenylphosphino)propane]dichloronickel(II) 、 2-氯甲苯 在 magnesium,hexane,chloride 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以16.40 g的产率得到cis-chloro(o-tolyl)(1,3-bis(diphenylphosphino)propane)nickel(II)
  参考文献：
  名称：

  π-Complexation in Nickel-Catalyzed Cross-Coupling Reactions

  摘要：

  The kinetic isotope effect (KIE) is used to experimentally elucidate the first irreversible step in oxidative addition reactions of a zerovalent nickel catalyst to a set of haloarene substrates. Halogenated o-methylbenzene, dimethoxybenzene, and thiophene derivatives undergo intramolecular oxidative addition through irreversible pi-complexation. Density functional theory computations at the B3LYP-D3/TZ2P-LANL2TZ(f)-LANL08d level predict eta(2)-bound pi-complexes are generally stable relative to a solvated catalyst plus free substrate and that ring-walking of the Ni(0) catalyst and intramolecular oxidative addition are facile in these intermediates.

  DOI：

  10.1021/jo402259z

文献信息

• Studies on the Generation of Metalating Species Equivalent to the Knochel–Hauser Base in the Dehydrobrominative Polymerization of Thiophene Derivatives
  作者：Shunsuke Tamba、Shinobu Mitsuda、Fujimaru Tanaka、Atsushi Sugie、Atsunori Mori

  DOI：10.1021/om201209z

  日期：2012.3.26

  Knochel–Hauser base TMPMgCl·LiCl, and head-to-tail-type regioregular poly(3-hexylthiophene) was obtained with high efficiency. The regioregular poly(3-hexylthiophene) was also found to be obtained by one-shot addition of 2-bromo-3-hexylthiophene as a monomer, magnesium amide, and a nickel catalyst, suggesting that complete formation of metalated thiophene species is not an essential requisite for the successful

  由LiTMP和MgBr 2形成的TMPMgBr·LiBr和（TMP）2 Mg·2LiBr进行了2-溴-3-己基噻吩的脱氢溴代缩聚反应，发现该替代物可以替代Knochel–Hauser碱TMPMgCl·LiCl和高效地获得了头到尾型区域规则的聚（3-己基噻吩）。还发现通过一次性添加2-溴-3-己基噻吩作为单体，酰胺化镁和镍催化剂来获得区域规则的聚（3-己基噻吩），这表明金属化噻吩物质的完全形成并非一成不变的。用镍催化剂成功聚合的必要条件。该方法被用于通过窄分子量分布的芳基制备甲苯基封端的聚噻吩，使用（邻甲苯基）NiCldppp作为催化剂。
• Externally Initiated Regioregular P3HT with Controlled Molecular Weight and Narrow Polydispersity
  作者：Hugo A. Bronstein、Christine K. Luscombe

  DOI：10.1021/ja9054977

  日期：2009.9.16

  The ability of chemists to design and synthesize :m-conjugated organic polymers with precise control remains the key to technological breakthroughs for using polymer materials in electronic and photonic devices. In this communication, the controlled chain-growth polymerization of regioregular poly (3-hexylthiophene) (P3HT) from an external initiator using 1,3-bis(diphenylphosphino)propane (dppp) as a catalyst ligand is reported. The complexes cis-chloro(phenyl)(dppp)nickel(II) and cis-chloro(o-tolyl)(dppp)nickel(II) were synthesized and characterized by P-31 NMR spectroscopy. These complexes served as initiators in the polymerization of 2-bromo-5chloromagnesio-3-hexylthiophene in THF at room temperature, affording fully regioregular P3HT with controlled molecular weights and narrow molecular weight distributions, as demonstrated by gel-permeation chromatography and H-1 NMR spectroscopy. MALDI-TOF mass spectrometry revealed that the polymers had almost complete incorporation of the initiating aryl group, and when the aryl group was o-tolyl, only Tol/H end groups were observed. Although external initiators have been used previously with a PPh3 ligand, that methodology led to polymers with broad molecular weight distributions. This is the first example in which complete control over the externally initiated P3HT polymerization has been achieved.