cyclopentadienylmolybdenum(II) (acetonitrile)2 (supine-η-butadiene)*BF4 | 203856-66-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: cyclopentadienylmolybdenum(II) (acetonitrile)2 (supine-η-butadiene)*BF4
• 英文别名: acetonitrile;buta-1,3-diene;cyclopenta-1,3-diene;molybdenum(2+);tetrafluoroborate
• CAS: 203856-66-0
• 化学式: BF₄*C₁₃H₁₇MoN₂
• 分子量: 384.036
• InChiKey: FZKGMWFPJGVRIF-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

• 作为产物：
  描述：

  乙腈 、 [Mo(η(5)-C5H5)(η(4)-butadiene)(CO)2](+)[BF4(-)] 在 Me₃NO 作用下， 以 乙腈 为溶剂， 以78%的产率得到cyclopentadienylmolybdenum(II) (acetonitrile)2 (supine-η-butadiene)*BF4
  参考文献：
  名称：

  Structural preferences of ν4-dienecyclopentadienyl complexes: molecular mechanics, molecular orbital and crystallographic studies

  摘要：

  DOI：

  10.1016/s0020-1693(97)06069-6

文献信息

• Cyclopentadienylmolybdenum(II) and -(III) Complexes Containing Diene and Allyl Ligands. 2. Comparative Reactivity of the Isomeric Complexes CpMo(η-C₃H₅)(η-C₄H₆) with Either <i>supine</i> or <i>prone</i> Allyl and Either <i>s-cis</i> (<i>Supine</i>) or <i>s-</i><i>trans</i> Butadiene Ligands toward Protons
  作者：Rinaldo Poli、Li-Sheng Wang

  DOI：10.1021/ja972587w

  日期：1998.4.1

  The electron-rich isomeric complexes CpMo(eta(3)-C3H5)(eta(4)-C4H6) (1a, prone-C3H5; supine-C4H6; 1b, supine-C3H5; supine-C4H6; 1c, supine-C3H5; s-trans-C4H6) do not react with neutral ligands under mild conditions. They are, however, easily protonated by a variety of different acids. Protonation of 1a and 1b involves attack at the terminal position of the allyl ligand and elimination of propene. Protonations with acetic acid show rates in the order 1a > 1b and afford the same product, CpMo(O2CCH3)(eta(4)-C4H6), 2, which can be oxidized to the 17-electron cation [2](+). HBF4 protonation of 1a in the absence of trapping donor molecules affords [CpMo(eta(4)-supine-C4H6)(mu-F2BF2)](n), 3. The latter readily reacts with donor molecules to afford [CpMo(eta(4)-supine-C4H6)L-2][BF4] products (L = MeCN, 4; (BuNC)-N-t, 5; or L-2 = 1,3-butadiene, 6), which are also directly and selectively obtained by protonation of 1a in the presence of the appropriate ligand. Compound 6 has a (supine-C4H6)(s-trans-C4H6) configuration and converts into compound 4 when dissolved in MeCN. Protonation of 1c is much slower relative to the isomers 1a and 1b. The observed products depend on the nature of the solvent. Protonation by HBF4 . Et2O in MeCN affords unstable [CpMo(supine-eta-C3H5)(syn-CH3-prone-eta-C3H4)(NCCH3)][BF4] (7), which rapidly exchanges the MeCN ligand. Decomposition of the latter involves a regioselective reductive coupling of the two allyl ligands to generate 3-methyl-1,5-hexadiene quantitatively. In C6D6, the HBF4 protonation of 1c produces small amounts of propene and a violet precipitate which gives a mixture of 4 and 7 upon treatment in MeCN. In the presence of 1,3-butadiene, protonation of 1c in THF followed by extraction into acetone affords a mixture of 6 and [CpMo(eta-C3H4-CH2CH2-eta-C3H4)(Me2CO)][BF4] (8). Compound 8 converts into [CpMo(eta-C3H4-CH2CH2-eta-C3H4)(L)][BF4] (L = MeCN, 9; PMe3, 10) when treated with the appropriate L. Protonation of 1c in MeCN in the presence of butadiene affords 7 which slowly decomposes, under these conditions, to a mixture of 4 and [CpMo(eta(4)-s-trans-C4H6)(MeCN)(2)](+), 11. The collective results for the protonation of 1c indicate that the proton attacks the s-trans diene ligand in MeCN. The preferred position of attack in nonpolar solvents, on the other hand, is the allyl. The difference of electronic distribution for isomers 1a-c has been investigated by DFT methods. The calculations indicate that the allyl ligand is a stronger donor in the supine configuration, while the diene ligand is both a weaker donor and a weaker acceptor when it is coordinated in the s-trans mode.