cyanide | 2122-47-6

• 分子结构分类: 有机化合物
• 英文名称: cyanide
• CAS: 2122-47-6
• 化学式: CN
• 分子量: 27.0067
• InChiKey: JEVCWSUVFOYBFI-OUBTZVSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  2.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  23.79
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  beryllium 、 [13C]氰化氢 以 gaseous matrix 为溶剂， 生成 cyanide 、 单氢化物铍 、
  参考文献：
  名称：

  激光烧蚀铍原子与氰化氢在过量氩气中的反应。BeCN、BeNC、HBeCN 和 HBeNC 的 FTIR 光谱和量子化学计算

  摘要：

  激光烧蚀的铍原子在 6-7 K 的过量氩气缩合过程中与氰化氢（H12CN、H13CN 和 D12CN）发生反应。在基质红外光谱中，观察到的主要产物是 BeNC、BeCN、HBeNC 和 HBeCN。与典型的铍键一致，这些新的铍物种是线性分子。对这些具有 BP86 泛函和 6-311G* 基组的产品的密度泛函理论计算非常好地预测了振动频率，即使对于 HBeCN，其中几乎等能的 Be-H 和 C⋮N 拉伸模式之间的混合会导致光谱中的严重并发症。尽管 B3LYP 和 MP2 计算比 BP86 方法更复杂，但它们几乎不能预测这些产品的振动频率。

  DOI：

  10.1021/ja970740g

文献信息

• Mechanisms of Catalyst Poisoning in Palladium-Catalyzed Cyanation of Haloarenes. Remarkably Facile C−N Bond Activation in the [(Ph₃P)₄Pd]/[Bu₄N]⁺ CN^- System
  作者：Stefan Erhardt、Vladimir V. Grushin、Alison H. Kilpatrick、Stuart A. Macgregor、William J. Marshall、D. Christopher Roe

  DOI：10.1021/ja078298h

  日期：2008.4.1

  Reaction paths leading to palladium catalyst deactivation during cyanation of haloarenes (eq 1) have been identified and studied. Each key step of the catalytic loop (Scheme 1) can be disrupted by excess cyanide, including ArX oxidative addition, X/CN exchange, and ArCN reductive elimination. The catalytic reaction is terminated via the facile formation of inactive [(CN)(4)Pd](2-), [(CN)(3)PdH](2-), and [(CN)(3)PdAr](2-). Moisture is particularly harmful to the catalysis because of facile CN- hydrolysis to HCN that is highly reactive toward Pd(0). Depending on conditions, the reaction of [(Ph3P)(4)Pd] with HCN in the presence of extra CN- can give rise to [(CN)(4)Pd](2-) and/or the remarkably stable new hydride [(CN)(3)PdH](2-) (NMR, X-ray). The X/CN exchange and reductive elimination steps are vulnerable to excess CN- because of facile phosphine displacement leading to stable [(CN)(3)PdAr](2-) that can undergo ArCN reductive elimination only in the absence of extra CN-. When a quaternary ammonium cation such as [Bu4N](+) is used as a phase-transfer agent for the cyanation reaction, C-N bond cleavage in the cation can occur via two different processes. In the presence of trace water, CN- hydrolysis yields HCN that reacts with Pd(0) to give [(CN)(3)PdH)(2-). This also releases highly active OH- that causes Hofmann elimination of [Bu4N](+) to give Bu3N, 1-butene, and water. This decomposition mode is therefore catalytic in H2O. Under anhydrous conditions, the formation of a new species, [(CN)(3)PdBu](2-), is observed, and experimental studies suggest that electron-rich mixed cyano phosphine Pd(0) species are responsible for this unusual reaction. A combination of experimental (kinetics, labeling) and computational studies demonstrate that in this case C-N activation occurs via an S(N)2-type displacement of amine and rule out alternative 3-center C-N oxidative addition or Hofmann elimination processes.