| 157045-32-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 157045-32-4
• 化学式: CF₃O₃S*C₁₈H₂₆N₃Pd
• 分子量: 539.915
• InChiKey: OGOAHVIXCQFWJP-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  、 一氧化碳 以 氘代丙酮 为溶剂， 生成 (2-methyl-1-benzoyl)(2,6-bis[(dimethylamino)methyl]pyridine)palladium trifluoromethanesulfonate
  参考文献：
  名称：

  一氧化碳插入带有三齿氮供体配体的阳离子单有机钯（II）配合物中的插入机理的高压NMR和从头算计算研究

  摘要：

  A number of methyl and arylpalladium(II) cations bearing tridentate nitrogen-donor ligands has been prepared, and their reactivity in the insertion of carbon monoxide has been studied. The resulting acetyl and aroylpalladium complexes of the ligands N-(2-picolyl)N,N',N'-trimethylethylenediamine (pico) and N,N,N',N '' N ''-pentamethyldiethylenetriamine (pmdeta) were isolated and characterized. In the case of the 4-nitrophenylpalladium and 2,4,6-trimethylphenylpalladium pico- and pmdeta complexes, no carbonylation products could be isolated. In these cases, either the equilibrium of the carbonylation reaction did not lie fully to the side of the insertion product even at 10 atm of CO or the insertion product decarbonylated upon attempted isolation. The methylpalladium complex of the 2,6-bis[(dimethylamino)methyl]pyridine (NN'N) ligand reacted quantitatively with CO in CD3-COCD3 to give acetic anhydride, palladium metal, and the protonated ligand; a mechanism for the anhydride formation is proposed. With the exception of the 1-naphthoyl derivative, the aroyl complexes of the NN'N ligand could not be isolated due to decarbonylation upon attempted isolation. Most of the unstable insertion products could, however, be characterized by IR and high-pressure NMR. Crystals of the 1-naphthoylpalladium complex with the NN'N ligand were obtained from acetone/pentane under a CO atmosphere. This complex is the first example of an aroylpalladium(II) cation. Two reaction pathways for the carbonyl insertion reaction, i.e., dissociative and associative, have been evaluated using H-1 NMR studies and ab initio calculations. The insertion reaction at 10 atm of CO pressure in CD3-COCD3 is complete within 2.5 min for most complexes, with the exception of those bearing strongly electron-withdrawing para substituents (e.g., NO2) or sterically demanding ortho substituents (e.g., 2,4,6-trimethyl) on the aryl ring. Ab initio calculations at the RHF, MP2//SCF, and CAS-SCF/CI levels on the cationic model system [Pd(CH3)(NH3)(3)](+) + CO and the neutral system [Pd(CH3)(2)(NH3)(2)] + CO show that the carbonylation reaction follows a hybrid pathway, i.e., a concerted replacement of NH3 by CO followed by migratory insertion of CO into the Pd-C bond instead of a purely dissociative or associative mechanism. For both the neutral and the cationic systems the rate-determining step is the migratory insertion. The insertion process is enhanced by coordination of the dissociated amine and is slightly more favorable in the neutral system. Together with the low-energy replacement of NH3 by CO, this implies that in both systems the rate of carbonyl insertion should be independent of the applied CO pressure.

  DOI：

  10.1021/om00012a032