| 158240-02-9

• CAS: 158240-02-9
• 化学式: C₁₇H₂₃CrN₂O
• 分子量: 323.378
• InChiKey: JGWDUCFHOQWLGL-UHFFFAOYSA-N

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 四氢呋喃 为溶剂， 生成 dicarbonyl(η5-cyclopentadienyl)nitrosylchromium 、
  参考文献：
  名称：

  Characteristic Physical and Chemical Properties of the 17-Valence-Electron Alkyl Complexes CpCr(NO)(L)R

  摘要：

  CpCr(NO)(L)R 17-valence-electron complexes (L = Lewis base, R = hydrocarbyl) are preparable from their iodo precursors by metathesis reactions. Their ESR spectra vary greatly in appearance, ranging from featureless singlets to more complicated spectra which reveal varying degrees of delocalization of the unpaired electron. For instance, the X-band ESR spectrum of the prototypal complex CpCr(NO)(PPh(3))(CH(2)SiMe(3)) in hexanes exhibits signals which indicate that the unpaired electron density is delocalized virtually over the entire molecule. Consistently, the solid-state molecular structure of CpCr(NO)(PPh(3))(CH(2)SiMe(3)) contains no unusual bond distances or angles, the intramolecular dimensions being comparable to those exhibited by related 18-electron CpCr(NO)-containing complexes. The redox properties of selected CpCr(NO)(L)R compounds have been established by cyclic voltammetry, and they reveal that these chromium species are difficult to reduce but relatively easy to oxidize. Neither the oxidation nor the reduction features display reversible behavior on the time scales of the cyclic voltammetry experiments, thereby indicating that these compounds decompose upon conversion to 16-electron cations or 18-electron anions and that the 17-valence-electron configuration is preferred. The chemical properties of the CpCr(NO)(L)R complexes reveal a degree of selective substitutional lability. Thus, CpCr(NO)(PPh(3))(CH(2)SiMe(3)) is inert to CO, H-2, and C2H4, but it does react with NO to produce the known CpCr(NO)(2)(CH(2)SiMe(3)) and with [NO]PF6 to form [CpCr(NO)(2)(PPh(3))]PF6, a previously inaccessible salt. Furthermore, treatment of CpCr(NO)(PPh(3))(CH(2)SiMe(3)) with 2 equiv of HSnPh(3) results in the loss of the alkyl group as Me(4)Si and subsequent addition of an Sn-H bond to the Cr center to produce CpCr(NO)(PPh(3))(H)(SnPh(3)). In solutions, the spectroscopic properties of the latter complex are consistent with it being a stannyl hydride species. However, its solid-state H-1 NMR spectrum and molecular structure suggest that as a solid it is best viewed as tending toward the eta(2)-stannane complex CpCr(NO)(PPh(3))(eta(2)-HSnPh(3)). Other CpCr(NO)(L)R complexes which are less sterically congested at the metal center than CpCr(NO)(PPh(3))(CH(2)SiMe(3)) react readily with CO to form CpCr(NO)(CO)(2) and CpCr(NO)(L)(CO).

  DOI：

  10.1021/om00010a039
• 作为产物：
  描述：

  哌啶 、 、 苄基氯化镁 在 碘甲烷 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以31%的产率得到
  参考文献：
  名称：

  Alkyl-for-Iodide Metathesis Initiated by Dissociation of the Phosphine Ligand from CpCr(NO)(PPh3)I

  摘要：

  The alkyl-for-iodide metathesis reaction that occurs when CpCr(NO)(PPh(3))I (1) is treated with 2 equiv of Me(3)SiCH(2)MgCl in THF to form CpCr(NO)(PPh(3))(CH(2)SiMe(3)) (6) has been investigated in some detail. The conversion is initiated by loss of the phosphine ligand from the chromium atom's coordination sphere, the most compelling evidence for this step being that addition of excess phosphine (e.g. 4 equiv) to the initial reaction mixture completely inhibits the reaction. Four intermediate complexes which are formed sequentially on the reaction path from 1 to 6 have been detected by IR and ESR spectroscopy. These complexes have been identified as CpCr(NO)(THF)I (2), CpCr-(NO-->Mg{CH(2)SiMe(3)})Cl)(THF)I (3), CpCr(NO-->Mg{CH(2)SiMe(3)}Cl)(THF)(CH(2)SiMe(3)) (4), and CpCr(NO) (THF)(CH(2)SiMe(3)) (5). Complexes 3 and 4 have also been detected spectroscopically during the reaction of CpCr(NO)(THF)I (2) with Me(3)SiCH(2)MgCl which produces CpCr(NO)(THF)(CH(2)SiMe(3)) (5). This understanding of the mechanistic pathway has resulted in the development of a general synthetic route to previously inaccessible 17-valence-electron CpCr(NO)(L)R complexes (L = C5H11N Or NH(2)CMe(3), R = CH(2)SiMe(3); L = C5H11N, R = CH(2)Ph).

  DOI：

  10.1021/ja00096a029