| 149730-36-9

• CAS: 149730-36-9
• 化学式: C₁₈H₁₀MnO₃*F₆P
• 分子量: 474.178
• InChiKey: VCRGESXQNNFQRU-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：

  在 1,8-bis(dimethylamino)naphthalene 作用下， 以 二氯甲烷-D2 为溶剂， 生成 (η(5)-cyclopenta[def]phenanthrenyl)Mn(CO)3
  参考文献：
  名称：

  Facile haptotropic shifts in organometallic complexes of 4H-cyclopenta[def]phenanthrene via naphthalene-type transition states: synthetic, x-ray crystallographic, NMR spectroscopic, and EHMO studies

  摘要：

  The tetracyclic system 4H-cyclopenta[def]phenanthrene (cppH) forms the complexes (eta6-cppH)Cr(CO)3 (2) and [(eta5-cppH)Mn(CO)3]PF6 (13); in both cases the metal is bonded to a terminal ring. Molecule 2 crystallizes in the orthorhombic space group Pbca, with a = 13.924(2) angstrom, b = 12.639(2) angstrom, c = 15.666(3) angstrom, and Z = 8. Deprotonation of 2 and 13 at room temperature yields [(eta5-cpp)Cr(CO)3]- (7) and (eta5-cpp)Mn(CO)3 (15), respectively, with no detectable zwitterionic intermediate. 15 crystallizes in the monoclinic space group P2(1)/c, with a = 11.274(2) angstrom, b = 8.752(2) angstrom, c = 14.404(3) angstrom, beta = 98.64(3)degrees, and Z = 4. The corresponding 8,9-dihydro-cpp derivatives (eta6-H-2-cppH)Cr(CO)3 (24) and [(eta6-H-2-cPPH)Mn(CO)3]PF6 (17) have also been prepared. 24 crystallizes in the orthorhombic space group Pbca, with a = 12.662(3) angstrom, b = 14.594(3) angstrom, c = 15.761(3), and Z = 8. Upon deprotonation, 17 yields an intermediate neutral complex (18) which undergoes an eta6-to-eta5-haptotropic shift only upon being heated to 60-degrees-C for 1 h. The whole process can be followed readily by NMR. The corresponding neutral intermediate derived by deprotonation of 13 can be trapped at -40-degrees-C. The relative ease of haptotropic shifts in the cpp complexes relative to the analogous H-2-CPP systems can be rationalized in terms of a transition state in which the migrating organometallic fragment is eta3-bonded to the polycyclic ligand such that a 10pi (naphthalene-like) character is retained.

  DOI：

  10.1021/ja00069a029
• 作为产物：
  描述：

  ammonium hexafluorophosphate 、 五羰基溴化锰(I) 、 4H-环五菲 在 AlCl₃ 作用下， 以 正己烷 为溶剂， 以61%的产率得到
  参考文献：
  名称：

  Facile haptotropic shifts in organometallic complexes of 4H-cyclopenta[def]phenanthrene via naphthalene-type transition states: synthetic, x-ray crystallographic, NMR spectroscopic, and EHMO studies

  摘要：

  The tetracyclic system 4H-cyclopenta[def]phenanthrene (cppH) forms the complexes (eta6-cppH)Cr(CO)3 (2) and [(eta5-cppH)Mn(CO)3]PF6 (13); in both cases the metal is bonded to a terminal ring. Molecule 2 crystallizes in the orthorhombic space group Pbca, with a = 13.924(2) angstrom, b = 12.639(2) angstrom, c = 15.666(3) angstrom, and Z = 8. Deprotonation of 2 and 13 at room temperature yields [(eta5-cpp)Cr(CO)3]- (7) and (eta5-cpp)Mn(CO)3 (15), respectively, with no detectable zwitterionic intermediate. 15 crystallizes in the monoclinic space group P2(1)/c, with a = 11.274(2) angstrom, b = 8.752(2) angstrom, c = 14.404(3) angstrom, beta = 98.64(3)degrees, and Z = 4. The corresponding 8,9-dihydro-cpp derivatives (eta6-H-2-cppH)Cr(CO)3 (24) and [(eta6-H-2-cPPH)Mn(CO)3]PF6 (17) have also been prepared. 24 crystallizes in the orthorhombic space group Pbca, with a = 12.662(3) angstrom, b = 14.594(3) angstrom, c = 15.761(3), and Z = 8. Upon deprotonation, 17 yields an intermediate neutral complex (18) which undergoes an eta6-to-eta5-haptotropic shift only upon being heated to 60-degrees-C for 1 h. The whole process can be followed readily by NMR. The corresponding neutral intermediate derived by deprotonation of 13 can be trapped at -40-degrees-C. The relative ease of haptotropic shifts in the cpp complexes relative to the analogous H-2-CPP systems can be rationalized in terms of a transition state in which the migrating organometallic fragment is eta3-bonded to the polycyclic ligand such that a 10pi (naphthalene-like) character is retained.

  DOI：

  10.1021/ja00069a029