| 229612-06-0

• CAS: 229612-06-0
• 化学式: C₆O₆V
• 分子量: 224.938
• InChiKey: BVSRFQDQORQURQ-VIURQLLDSA-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：

  以 solid matrix 为溶剂， 生成 、
  参考文献：
  名称：

  Morton; Preston, Organometallics, 1984, vol. 3, # 9, p. 1386 - 1388

  摘要：

  DOI：
• 作为产物：
  描述：

  [n-Bu4N][V(13CO)6] 在 HCl 作用下， 以 neat (no solvent) 为溶剂， 生成
  参考文献：
  名称：

  D_3d Ground-State Structure of V(CO)₆:  A Combined Matrix Isolation and ab Initio Study of the Jahn−Teller Effect

  摘要：

  Structures, relative energies, vibrational spectra, and ESR parameters of the 17e(-) molecule V(CO)(6) in O-h, D-3d, D-4h, and D-2h symmetry have been computed with density functional and high-level ab initio methods. At all theoretical levels applied, the same energetic order is obtained, D-3d < D-2h < D-4h < O-h, with the D-2h structure as a transition state connecting equivalent D-3d species. At the RCCSD(T)/AE2 level using UBP86/AE2 geometries, the energies of the D-2h, D-4h and O-h species relative to that of D-3d minimum are predicted to be 210, 535, and 731 cm(-1), respectively. According to molecular dynamics simulations on the UBP86/AE1 potential energy surface, the D3d minimum is preserved at very low temperatures (around 16 K), whereas at 300 K the molecule is highly fluxional with an averaged structure indistinguishable from that of [V(CO)6](-) with its O-h symmetric ground state. Nearly complete IR and Raman spectra Of V(CO)(6) and V((CO)-C-13)(6) have been recorded at 300 K for the first time in the gas phase, in solution, and at cryogenic temperatures in Ne and Ar matrices. The spectra show a pronounced temperature dependence, especially for the Jahn-Teller active modes, E-g and T-2g. The observed infrared matrix spectra generally agree well with the calculated spectrum (BP86/AE2 level) for the D-3d structure and much less with that of the D-4h isomer. The A(1g) modes in the Raman spectra are reasonably well reproduced computationally in the harmonic approximation, whereas this approximation breaks down for the E-g and T-2g bands, as expected. Further evidence for the D-3d symmetry Of V(CO)(6) is obtained from a reanalysis of the experimental ESR spectrum that is reported in the literature. The observed ordering of the hyperfine coupling constants A(\\) and A(perpendicular to) is reproduced theoretically only when distortion to D-3d symmetry is assumed. In addition, the bonding properties Of V(CO)(6) are compared to those Of [V(CO)6](-) and Cr(CO)(6).

  DOI：

  10.1021/jp021835u

文献信息

• Oxidation Products of Vanadocene and of Its Permethylated Analogue, Including the Isolation and the Reactivity of the Unsolvated [VCp₂]⁺ Cation
  作者：Fausto Calderazzo、Isabella Ferri、Guido Pampaloni、Ulli Englert

  DOI：10.1021/om9809320

  日期：1999.6.1

  the μ-isocarbonyl derivative Cp2V(μ-OC)V(CO)5 as a transient species, which has been characterized in solution by IR analysis. By reaction of VCp2 with V(13CO)6 followed by treatment with 12CO, the ionic dicarbonyl derivative [VCp2(12CO)2][V(13CO)6] is formed, thus showing that during the formation of the ionic compound no redistribution of the carbonyl ligands between the two metal centers occurs.

  在甲苯中通过[FeCp 2 ] +对钒氧杂环丁烯VCp 2进行单电子氧化可得到14电子[VCp 2 ] +阳离子，该阳离子已首次作为非溶剂化物质被分离出来。六羰基钒与VCp 2反应生成μ-异羰基衍生物Cp 2 V（μ-OC）V（CO）5作为过渡物种，已在溶液中通过IR分析对其进行了表征。通过使VCp 2与V（13 CO）6反应，然后用12 CO处理，离子二羰基衍生物[VCp 2（12 CO）2形成] [V（13 CO）6 ]，因此表明在形成离子化合物期间，在两个金属中心之间未发生羰基配体的重新分布。双（环戊二烯基）钒（II）和Co 2（CO）8得到Cp 2 VCo（CO）4，即使在低温下也能在溶液中缓慢分解，得到[VCp 2（CO）2 ] [Co（CO）4 ] ，这是通过常规方法确定的，包括单晶X射线衍射。未溶剂化的[VCp 2 ] +的反应性 据报道，阳离子以及含有钒和钴以及几种路易斯碱的杂双金属化合物也是如此。