(η(2),η(2)-3,6-dimethylene-1,7-butadiene)NiPiCy3 | 163976-21-4

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: (η(2),η(2)-3,6-dimethylene-1,7-butadiene)NiPiCy3
• CAS: 163976-21-4
• 化学式: C₁₀H₁₄*C₁₈H₃₃P*Ni
• 分子量: 473.345
• InChiKey: OFCVRVUQCGAYQS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.71
• 重原子数：
  30.0
• 可旋转键数：
  8.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)nickel (0) 、 3,6-Dimethylen-1,7-octadien 、 三环己基膦 以 乙醚 为溶剂， 以66%的产率得到(η(2),η(2)-3,6-dimethylene-1,7-butadiene)NiPiCy3
  参考文献：
  名称：

  Interaction of Acyclic Tetraenes and Trienes with Transition Metals: Organonickel Compounds

  摘要：

  The tetraene 3,6-dimethylene-1,7-octadiene (DMOD) reacts with zerovalent [NiPR(3)] species to give (eta(2),eta(2)-DMOD)NiPR(3) in which the methylene group of one 1,3-diene fragment and the vinyl group of the second interact with the metal atom. This unsymmetrical complexation of the tetraene has been confirmed by X-ray diffraction for the P(OC6H4-o-Ph)(3)-stabilized derivative (space group P2(1)/c, a = 10.057(1) Angstrom, b = 36.196(1) Angstrom, c = 10.944(1) Angstrom, a = y = 90 degrees, beta = 105.76(1)degrees, Z = 4, R = 0.056, R(W) = 0.071) and is the result of the preferred coordination of a 1,6-heptadiene chain to the metal atom. The NMR spectra indicate that the molecule is fluxional with a pairwise exchange of the methylene groups and of the vinyl groups. The structure of the product formed in the presence of the bidentate ligands (Pr2P)-P-i(CH2)(n)PPr2i (n = 1, 2, 3) is dependent upon the length of the chain bridging the two P-atoms, and compounds have been isolated having the composition (eta(2),eta(2),eta(2),eta(2)-DMOD)Ni-2(Pr-2(i)- PCH2PPr2i), (eta(4),eta(4)-DMOD)[Ni((Pr2PC2H4PPr2i)-P-i)](2), and (eta(2),eta(2)-DMOD)[Ni((Pr2PC3H6PPr)-P-i(2)(i))](2). The molecular structure of the bis(diisopropylphosphino)ethane-containing compound has been established by X-ray diffraction (space group C2/c, a = 17.535(2) Angstrom, b = 24.152(1) Angstrom, c = 11.767(1) Angstrom, a = y = 90 degrees, beta = 120.65(1)degrees, Z = 4, R = 0.034, R(W) = 0.035) and confirms that the two 1,3-diene fragments of the tetraene interact with [Ni((Pr2PC2H4PPr2i)-P-i)] moieties. The trienes 3-methylene-1,6-heptadiene and 3-methylene-1,7-octadiene react with [NiPPr3i] species to give (eta(2),eta(2)-triene)NiPPr3i compounds in which a 1,6-heptadiene chain is complexed to the metal atom.

  DOI：

  10.1021/om00004a049