| 188842-44-6

• CAS: 188842-44-6
• 化学式: C₅H₅CrI₂NO*C₁₆H₃₆N
• 分子量: 643.374
• InChiKey: LGNSHEKKDXXIHN-UHFFFAOYSA-L

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

• 作为产物：
  描述：

  、 四丁基碘化铵 以 二氯甲烷 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  Synthesis and Characterization of 17-Valence-Electron [CpCr(NO)X₂]^- Anions:  Oxidatively Induced Loss of the Nitrosyl Ligand¹

  摘要：

  Several anionic and paramagnetic [CpCr(NO)X-2](-) complexes (X = I [1], O3SCF3 (OTf) [2], Br [3], Cl [4]) have been prepared as potential precursors to neutral CpCr(NO)X-2 species. Reaction of [CpCr(NO)I](2) with [NBu4]I provides [NBu4][1], and halide abstraction from [NBu4][1] with 2 equiv of AgOTf affords [NBu4][2]. The weakly-bound OTf- ligands of [NBu4][2] are readily displaced by Br- to produce [NBu4][3]. The dichloro complexes [NEt4][4] and [PPN][4] are obtained by treating [CpCr(NO)Cl](2) with [NE4]Cl and [PPN]Cl, respectively. Use of acetonitrile as reaction solvent allows generation of the requisite [CpCr(NO)Cl](2) directly from CpCr(NO)(CO)(2) and PCl5, a marked improvement over previous synthetic routes to this dimer. Similar halogenations of Cp*Cr(NO)(CO)(2) in NCMe provide access to the previously unknown [Cp*Cr(NO)I](2) (5), and [Cp*Cr(NO)Cl](2) (6), halo-bridged, and dimers. The solid-state molecular structure of [PPN][4]. CH2Cl2 has been established by single-crystal X-ray crystallography to be a normal three-legged piano stool. The one-electron oxidation of [4] has been investigated both chemically (by reaction with [Cp2Fe](+)) and electrochemically (by cyclic voltammetry). These studies suggest that upon oxidation a high-spin CpCr(NO)Cl-2 complex is initially formed which then rapidly releases NO. Extended Huckel molecular-orbital calculations have been performed on [4], [CpCr(CO)(3)](-), and [CpCrCl3](-), three CpCr-containing anions with ligands of varying pi-bonding capabilities. Correlations between their orbital energies and electron occupancies and a rationale for the lability of the NO ligand in neutral CpCr(NO)Cl-2 are provided.

  DOI：

  10.1021/ja963464z