N-methyl-N'-(2-pyridylmethyl)imidazolium hexafluorophosphate | 501926-28-9

• 英文名称: N-methyl-N'-(2-pyridylmethyl)imidazolium hexafluorophosphate
• 英文别名: 3-methyl-1-(pyridin-2-ylmethyl)imidazolium hexafluorophosphate
• CAS: 501926-28-9
• 化学式: C₁₀H₁₂N₃*F₆P
• 分子量: 319.19
• InChiKey: NTBMIOXLIKDMHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  N-methyl-N'-(2-pyridylmethyl)imidazolium hexafluorophosphate 、 镍 在 air 作用下， 以 乙腈 为溶剂， 以69%的产率得到bis(3-methyl-1-(pyridin-2-ylmethyl)imidazolylidene)nickel(II) hexafluorophosphate
  参考文献：
  名称：

  Carbene Transfer Reactivities of Nickel(II)–N-Heterocyclic Carbene Complexes and Their Applications in the Synthesis of Metal–NHC Complexes

  摘要：

  We describe a new synthetic procedure for transition-metal N-heterocyclic carbene complexes A number of Pd(II), Pt(II), Co(III), and Ru(II) complexes containing functionalized NHCs have been obtained in good to excellent yields using Ni-II-NHC complexes as carbene transfer reagents. Ni-II-NHC complexes are easily prepared from the direct reactions of the corresponding imidazolium salts with commercially available Raney nickel powder. The byproduct of transmetalation reactions, NiCl2, can be easily removed by simple filtration. This study offers a new, economical, and practical synthetic method for metal-NHC complexes.

  DOI：

  10.1021/om200881s

文献信息

• An Anion-Dependent Switch in Selectivity Results from a Change of C−H Activation Mechanism in the Reaction of an Imidazolium Salt with IrH₅(PPh₃)₂
  作者：Leah N. Appelhans、Daniele Zuccaccia、Anes Kovacevic、Anthony R. Chianese、John R. Miecznikowski、Alceo Macchioni、Eric Clot、Odile Eisenstein、Robert H. Crabtree

  DOI：10.1021/ja055317j

  日期：2005.11.23

  counteranion along the series Br, BF4, PF6, SbF6 in their ion-paired 2-pyridylmethyl imidazolium salts causes the kinetic reaction products with IrH5(PPh3)2 to switch from chelating N-heterocyclic carbenes (NHCs) having normal C2 (N path) to abnormal C5 binding (AN path). Computational work (DFT) suggests that the AN path involves C-H oxidative addition to Ir(III) to give Ir(V) with little anion dependence. The

  改变 Br、BF4、PF6、SbF6 在其离子对 2-吡啶甲基咪唑鎓盐中的抗衡阴离子会导致与 IrH5(PPh3)2 的动力学反应产物从螯合 N-杂环卡宾 (NHCs) 转换为具有正常 C2 (N路径）到异常 C5 绑定（AN 路径）。计算工作 (DFT) 表明 AN 路径涉及 CH 氧化加成到 Ir(III) 以产生 Ir(V)，而阴离子依赖性很小。相比之下，N 路径通过异裂 CH 激活，质子转移到相邻的氢化物。转移的质子伴随着阴离子耦合质子转移中的抗衡阴离子，导致 N 路径的阴离子依赖性，从而导致 N/AN 选择性。N 路径通过 Ir(III)，而不是 Ir(V)，因为正常 NHC 是比异常 NHC 强得多的供体配体。PGSE NMR 实验支持在反应物和产物中形成离子对。19F,1H-HOESY NMR 实验表明产物的离子对结构与计算预测(ONIOM(B3PW91/UFF))一致。