(Me2Al[(μ-N(t)Bu)2P(.mu2-N(t)Bu)2(μ2-THF)[Li(THF)]2) | 863591-20-2

• 英文名称: (Me2Al[(μ-N(t)Bu)2P(.mu2-N(t)Bu)2(μ2-THF)[Li(THF)]2)
• CAS: 863591-20-2
• 化学式: C₃₀H₆₆AlLi₂N₄O₃P
• 分子量: 602.716
• InChiKey: ULGIPJUBLJMTNY-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：

  (Me2Al[(μ-N(t)Bu)2P(.mu2-N(t)Bu)2(μ2-THF)[Li(THF)]2) 在 iodine 作用下， 以 四氢呋喃 为溶剂， 生成 (Me2Al[(μ-N(t)Bu)2P(μ-N(t)Bu)2]Li(THF)2)
  参考文献：
  名称：

  Synthesis and Structures of Aluminum and Magnesium Complexes of Tetraimidophosphates and Trisamidothiophosphates:  EPR and DFT Investigations of the Persistent Neutral Radicals {Me₂Al[(μ-NR)(μ-N^tBu)P(μ-N^tBu)₂]Li(THF)₂}^• (R = SiMe₃, ^tBu)

  摘要：

  Reactions of (RNH)(3)PNSiMe3 (3a, R = Bu-t; 3b, R = Cy) with trimethylaluminum result in the formation of {Me-2-Al[(mu-(NBu)-Bu-t)(mu-NSiMe3)P((NHBu)-Bu-t)(2)]} (4) and the dimeric trisimidometaphosphate {Me2Al[(mu-NCy)(mu-NSiMe3)P(mu-NCy)(2)P-(mu-NCy)(mu-NSiMe3)]AIMe(2)} (5a), respectively. The reaction of SP((NHBu)-Bu-t)(3) (2a) with 1 or 2 equiv of AIMe(3) yields {Me2Al[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)]} (7) and {Me2Al[(mu-S)(mu-(NBu)-Bu-t)P(mu-(NHBu)-Bu-t)(mu-(NBu)-Bu-t)]AlMe2} (8), respectively. Metalation of 4 with (BuLi)-Bu-n produces the heterobimetallic species {Me2Al[(mu-(NBu)-Bu-t)(mu-NSiMe3)P(mu-(NHBu)-Bu-t)(mu-(NBu)-Bu-t)]-Li(THF)(2)} (9a) and {[Me2Al][Li](2)[P((NBu)-Bu-t)(3)(NSiMe3)]} (10) sequentially; in THF solutions, solvation of 10 yields an ion pair containing a spirocyclic tetraimidophosphate monoanion, Similarly, the reaction of ((BuNH)-Bu-t)(3)(PNBu)-Bu-t with AIMe(3) followed by 2 equiv of (BuLi)-Bu-n generates {Me2Al[(mu-(NBu)-Bu-t)(2)(mu(2)-(NBu)-Bu-t)(2)(mu(2)-THF)[Li(THF)](2)} (11a), Stoichiometric oxidations of 10 and 11a with iodine yield the neutral spirocyclic radicals {Me2Al[(mu-NR)(mu-(NBu)-Bu-t)P(mu-(NBu)-Bu-t)(2)]Li-(THF)(2)}(center dot) (13a, R = SiMe3; 14a, R = Bu-t), which have been characterized by electron paramagnetic resonance spectroscopy. Density functional theory calculations confirm the retention of the spirocyclic structure and indicate that the spin density in these radicals is concentrated on the nitrogen atoms of the PN2Li ring, When 3a or 3b is treated with 0.5 equiv of dibutylmagnesium, the complexes {Mg[(mu-(NBu)-Bu-t)(mu-(NHBu)-Bu-t)P((NHBu)-Bu-t)(NSiMe3)](2)} (15) and {Mg[(mu-NCy)(mu-NSiMe3)P(NHCy)(2)](2)} (16) are obtained, respectively. The addition of 0.5 equiv of MgBu2 to 2a results in the formation of {Mg[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)](2)} (17), which produces the hexameric species {[MgOH]-[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)]}(6) (18) upon hydrolysis. Compounds 4, 5a, 7-11a, and 15-17 have been characterized by multinuclear (H-1, C-13, and P-31) NMR spectroscopy and, in the case of 5a, 9a center dot 2THF, 11a, and 18, by X-ray crystallography.

  DOI：

  10.1021/ic050689e
• 作为产物：
  描述：

  ((t)BuNH)3PN(t)Bu 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 生成 (Me2Al[(μ-N(t)Bu)2P(.mu2-N(t)Bu)2(μ2-THF)[Li(THF)]2)
  参考文献：
  名称：

  Synthesis and Structures of Aluminum and Magnesium Complexes of Tetraimidophosphates and Trisamidothiophosphates:  EPR and DFT Investigations of the Persistent Neutral Radicals {Me₂Al[(μ-NR)(μ-N^tBu)P(μ-N^tBu)₂]Li(THF)₂}^• (R = SiMe₃, ^tBu)

  摘要：

  Reactions of (RNH)(3)PNSiMe3 (3a, R = Bu-t; 3b, R = Cy) with trimethylaluminum result in the formation of {Me-2-Al[(mu-(NBu)-Bu-t)(mu-NSiMe3)P((NHBu)-Bu-t)(2)]} (4) and the dimeric trisimidometaphosphate {Me2Al[(mu-NCy)(mu-NSiMe3)P(mu-NCy)(2)P-(mu-NCy)(mu-NSiMe3)]AIMe(2)} (5a), respectively. The reaction of SP((NHBu)-Bu-t)(3) (2a) with 1 or 2 equiv of AIMe(3) yields {Me2Al[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)]} (7) and {Me2Al[(mu-S)(mu-(NBu)-Bu-t)P(mu-(NHBu)-Bu-t)(mu-(NBu)-Bu-t)]AlMe2} (8), respectively. Metalation of 4 with (BuLi)-Bu-n produces the heterobimetallic species {Me2Al[(mu-(NBu)-Bu-t)(mu-NSiMe3)P(mu-(NHBu)-Bu-t)(mu-(NBu)-Bu-t)]-Li(THF)(2)} (9a) and {[Me2Al][Li](2)[P((NBu)-Bu-t)(3)(NSiMe3)]} (10) sequentially; in THF solutions, solvation of 10 yields an ion pair containing a spirocyclic tetraimidophosphate monoanion, Similarly, the reaction of ((BuNH)-Bu-t)(3)(PNBu)-Bu-t with AIMe(3) followed by 2 equiv of (BuLi)-Bu-n generates {Me2Al[(mu-(NBu)-Bu-t)(2)(mu(2)-(NBu)-Bu-t)(2)(mu(2)-THF)[Li(THF)](2)} (11a), Stoichiometric oxidations of 10 and 11a with iodine yield the neutral spirocyclic radicals {Me2Al[(mu-NR)(mu-(NBu)-Bu-t)P(mu-(NBu)-Bu-t)(2)]Li-(THF)(2)}(center dot) (13a, R = SiMe3; 14a, R = Bu-t), which have been characterized by electron paramagnetic resonance spectroscopy. Density functional theory calculations confirm the retention of the spirocyclic structure and indicate that the spin density in these radicals is concentrated on the nitrogen atoms of the PN2Li ring, When 3a or 3b is treated with 0.5 equiv of dibutylmagnesium, the complexes {Mg[(mu-(NBu)-Bu-t)(mu-(NHBu)-Bu-t)P((NHBu)-Bu-t)(NSiMe3)](2)} (15) and {Mg[(mu-NCy)(mu-NSiMe3)P(NHCy)(2)](2)} (16) are obtained, respectively. The addition of 0.5 equiv of MgBu2 to 2a results in the formation of {Mg[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)](2)} (17), which produces the hexameric species {[MgOH]-[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)]}(6) (18) upon hydrolysis. Compounds 4, 5a, 7-11a, and 15-17 have been characterized by multinuclear (H-1, C-13, and P-31) NMR spectroscopy and, in the case of 5a, 9a center dot 2THF, 11a, and 18, by X-ray crystallography.

  DOI：

  10.1021/ic050689e