tetrabutylammonium cyanide-(13)C | 924275-74-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: tetrabutylammonium cyanide-(13)C
• 英文别名: [Bu4N](13)CN
• CAS: 924275-74-1
• 化学式: C₁₆H₃₆N*CN
• 分子量: 269.475
• InChiKey: KRRBFUJMQBDDPR-IEOVAKBOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  19.0
• 可旋转键数：
  12.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  23.79
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  四(三苯基膦)钯 、 tetrabutylammonium cyanide-(13)C 以 not given 为溶剂， 生成 [Bu₄N]2[(N⁽¹³⁾C)3Pd(H)]
  参考文献：
  名称：

  Why Excess Cyanide Can Be Detrimental to Pd-Catalyzed Cyanation of Haloarenes. Facile Formation and Characterization of [Pd(CN)₃(H)]^2- and [Pd(CN)₃(Ph)]^2-

  摘要：

  DOI：

  10.1021/ja066931d
• 作为产物：
  描述：

  POTASSIUM CYANIDE-13C 、 四丁基氢氧化铵 以 四氢呋喃 为溶剂， 反应 24.0h， 以92%的产率得到tetrabutylammonium cyanide-(13)C
  参考文献：
  名称：

  Mechanisms of Catalyst Poisoning in Palladium-Catalyzed Cyanation of Haloarenes. Remarkably Facile C−N Bond Activation in the [(Ph₃P)₄Pd]/[Bu₄N]⁺ CN^- System

  摘要：

  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.

  DOI：

  10.1021/ja078298h

文献信息

• Change in Electron Configuration of Ferric Ion in Bis(cyanide)(<i>meso</i>-tetraalkylporphyrinatoiron(III)), [Fe(T<i>R</i>P)(CN)₂]^-, Caused by the Nonplanarity of the Porphyrin Ring
  作者：Mikio Nakamura、Takahisa Ikeue、Hiroshi Fujii、Tetsuhiko Yoshimura

  DOI：10.1021/ja970602r

  日期：1997.7.1

  [Fe(TEtP)(CN)2]-, and [Fe(TiPrP)(CN)2]-, respectively. Corresponding to the pyrrole proton signal, the cyanide carbon signal also exhibits a large downfield shift. The difference in chemical shifts between [Fe(THP)(CN)2]- and [Fe(TiPrP)(CN)2]- reaches as much as 1443 ppm at −25 °C. The substituent dependent phenomena are also observed in EPR spectra taken in frozen CH2Cl2 solution at 4.2 K. While the unsubstituted

  报道了一系列双（氰化物）（内消旋四烷基卟啉 (III)）、[Fe(TRP)(CN)2]- 其中 R 是 H、Me、Et 和 iPr 的合成和表征。未取代的 [Fe(THP)(CN)2]- 的 1H NMR 光谱显示 CD2Cl2 中 δ = -23.19 ppm (-25 °C) 处的吡咯信号，这是非常典型的低自旋铁络合物。随着内消旋取代基的体积增加，吡咯信号向低磁场移动；[Fe(TMeP)(CN)2]-、[Fe(TEtP)(CN)2]- 和 [Fe(TiPrP)(CN)2]- 分别为 0.34、-2.26 和 11.94 ppm。对应于吡咯质子信号，氰化物碳信号也表现出大的低场位移。[Fe(THP)(CN)2]- 和 [Fe(TiPrP)(CN)2]- 之间的化学位移差异在 -25 °C 时高达 1443 ppm。
• Catalytic Reduction of Cyanide to Ammonia and Methane at a Mononuclear Fe Site
  作者：Christian M. Johansen、Jonas C. Peters

  DOI：10.1021/jacs.3c12395

  日期：2024.2.28

  of CN– reduction, including iron isocyanides (P3SiFeCNH+/0) and terminal iron aminocarbynes (P3SiFeCNH2+/0). Aminocarbynes are isoelectronic to iron hydrazidos (Fe═N–NH2+/0), which have been invoked as selectivity-determining intermediates of N2R (NH3 versus N2H4 products). For the present CN– reduction catalysis, reduction of aminocarbyne P3SiFeCNH2+ is proposed to be rate but not selectivity contributing

  固氮酶催化氮还原 （N2R） 为氨，以及非天然底物的还原，包括 7H+/6e– 将氰化物还原为 CH4 和 NH3。CN– 和 N2 是等电子的，因此比较能够同时还原 CN– 和 N2 的合成 Fe 催化剂的机理是很有趣的。在这里，我们描述了通过高选择性 （P3Si）Fe（CN） 催化剂（P3Si 代表三（膦）硅烷基配体）将 CN– 催化还原为 NH3 和 。在过量的酸 （[Ph2NH2]OTf） 和还原剂 （（C6H6）2Cr） 存在下驱动催化，证明周转率高达 73。该催化剂体系对 N2R 也具有适度的处理能力，并且在结构上与其他基于三（膦）Fe 的 N2R 催化剂相关。催化剂和还原剂的选择对于观察高产率很重要。机理研究阐明了 CN– 还原的几种中间体，包括异氰化铁 （P3SiFeCNH+/0） 和末端氨基甲炔铁 （P3SiFeCNH2+/0）。氨基炙与肼酰铁 （Fe═N–NH2+/0）
• [EN] MAGNETODYNAMIC ACTIVATION OF 13C-ACYL ISONIAZID AND ISONIAZID AND ETHIONAMIDE DERIVATIVES<br/>[FR] ACTIVATION MAGNÉTODYNAMIQUE DE 13C-ACYL-ISONIAZIDE ET DE DÉRIVÉS D'ISONIAZIDE ET D'ÉTHIONAMIDE
  申请人：STC UNM

  公开号：WO2014039829A2

  公开（公告）日：2014-03-13
• ¹³C NMR Signal Detection of Iron-Bound Cyanide Ions in Ferric Cyanide Complexes of Heme Proteins
  作者：Hiroshi Fujii

  DOI：10.1021/ja025737y

  日期：2002.5.1

  13CN ion appears to have the greatest potential to probe the heme environment of the ferric heme proteins; however, a resonance of the iron-bound (13)CN ion in ferric heme proteins has not yet been located. We show here the first detection of (13)C NMR signals of the iron-bound (13)CN for heme proteins and their model complexes in an unexpectedly large upfield region. This study demonstrates that the (13)C NMR signal of the iron-bound (13)CN is a sensitive probe to study the nature of the proximal ligand in ferric heme protein.