trans-chloro(3-hydro-1-methyl-3-pyridylidene)bis(triphenylphosphine)nickel(II) triflate | 1255923-04-6

• 英文名称: trans-chloro(3-hydro-1-methyl-3-pyridylidene)bis(triphenylphosphine)nickel(II) triflate
• 英文别名: 1-methyl-3H-pyridin-1-ium-3-ide;nickel(2+);trifluoromethanesulfonate;triphenylphosphane;chloride
• CAS: 1255923-04-6
• 化学式: CF₃O₃S*C₄₂H₃₇ClNNiP₂
• 分子量: 860.923
• InChiKey: XLXYCRIPDAOIQZ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.25
• 重原子数：
  55
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  68.6
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  四(三苯基膦)镍 、 3-chloro-1-methylpyridinium triflate 以 四氢呋喃 为溶剂， 以49.6%的产率得到trans-chloro(3-hydro-1-methyl-3-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