2,4-dichloro-1-methylpyridinium triflate | 1255923-06-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 2,4-dichloro-1-methylpyridinium triflate
• CAS: 1255923-06-8
• 化学式: CF₃O₃S*C₆H₆Cl₂N
• 分子量: 312.097
• InChiKey: ZGAFTOIQEAWGAM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.87
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  61.08
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  四(三苯基膦)镍 、 2,4-dichloro-1-methylpyridinium triflate 以 四氢呋喃 为溶剂， 以62.4%的产率得到trans-chloro(2-chloro-4-hydro-1-methyl-4-pyridylidene)bis(triphenylphosphine)nickel(II) triflate
  参考文献：
  名称：

  Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

  摘要：

  We report a thorough investigation of a series of isomeric complexes with the general formula trans-(pyridylidene)M(PPh3)(2)Cl (M = Pd, Ni). For the first time, a systematic comparison of normal, abnormal, and remote bonding modes is presented. X-ray structural and C-13 NMR data indicate the importance of carbenoid mesomeric contributions in their compound class.. The catalytic performance of the palladium complexes trans-(pyridylidene)Pd(PPh3)(2)Cl as precursors in Suzuki-Miyaura-type cross-coupling suggests a correlation of remote bonding with catalyst robustness and effectivity. When metal precursors M(PPh3)(4) are reacted with 2,4-dichloropyridinium salts, preferential formation of remote carbene complexes occurs and indications are that electronic parameters rather than steric influences are responsible for the observed selectivity. Calculations at the BP86/TZ2P level of theory support interpretation of the results.

  DOI：

  10.1021/om100431u
• 作为产物：
  描述：

  2,4-二氯吡啶 、 三氟甲烷磺酸甲酯 以 二氯甲烷 为溶剂， 反应 18.0h， 以99.8%的产率得到2,4-dichloro-1-methylpyridinium triflate
  参考文献：
  名称：

  Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

  摘要：

  We report a thorough investigation of a series of isomeric complexes with the general formula trans-(pyridylidene)M(PPh3)(2)Cl (M = Pd, Ni). For the first time, a systematic comparison of normal, abnormal, and remote bonding modes is presented. X-ray structural and C-13 NMR data indicate the importance of carbenoid mesomeric contributions in their compound class.. The catalytic performance of the palladium complexes trans-(pyridylidene)Pd(PPh3)(2)Cl as precursors in Suzuki-Miyaura-type cross-coupling suggests a correlation of remote bonding with catalyst robustness and effectivity. When metal precursors M(PPh3)(4) are reacted with 2,4-dichloropyridinium salts, preferential formation of remote carbene complexes occurs and indications are that electronic parameters rather than steric influences are responsible for the observed selectivity. Calculations at the BP86/TZ2P level of theory support interpretation of the results.

  DOI：

  10.1021/om100431u

文献信息

• Amine-substituted α-N(standard)- and δ-N(remote)-pyridylidene complexes: Synthesis and bonding
  作者：Elzet Stander-Grobler、Christoph E. Strasser、Oliver Schuster、Stephanie Cronje、Helgard Raubenheimer

  DOI：10.1016/j.ica.2011.05.038

  日期：2011.10

  Reaction of ortho-amino-para-chloro- and ortho-chloro-para-amino-pyridinium triflate with tetrakis(triphenylphosphine) complexes of Ni or Pd afforded by oxidative substitution compounds that can be represented as cationic carbene complexes. NMR as well as X-ray structural studies revealed the role played by the NMe2 and M(PPh)(2)Cl (M = Ni or Pd) substituents in stabilizing the complexes by pi-retro-donation and, consequently, in governing the relative importance of certain mesomeric representations describing their structures. (C) 2011 Elsevier B.V. All rights reserved.