[6-Di(propan-2-yl)phosphanyl-1,2-dihydroacenaphthylen-5-yl]-methyl-phenylphosphane | 1440433-80-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: [6-Di(propan-2-yl)phosphanyl-1,2-dihydroacenaphthylen-5-yl]-methyl-phenylphosphane
• CAS: 1440433-80-6
• 化学式: C₂₅H₃₀P₂
• 分子量: 392.461
• InChiKey: LLUJUTRXWNVZSJ-UHFFFAOYSA-N

物化性质

• 沸点：
  509.4±50.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (bicyclo[2.2.1]hepta-2,5-diene)tetracarbonylmolybdenum(0) 、 [6-Di(propan-2-yl)phosphanyl-1,2-dihydroacenaphthylen-5-yl]-methyl-phenylphosphane 以 二氯甲烷 为溶剂， 反应 16.0h， 以23%的产率得到
  参考文献：
  名称：

  peri-Substituted Phosphino-Phosphonium Salts: Synthesis and Reactivity

  摘要：

  The clean reaction of 5-lithio-6-(diisopropylphosphino)acenaphthene with dichlorophosphines RPCl2 gives the peri-substituted phosphino-phosphonium salts [Acenap(PiPr(2))(PR)]Cl-+(-) (2, R = Ph; 3, R = Fc; 4, R = NMe2; 5, R = iPr; Acenap = acenaphthene-5,6-diyl). Their ionic structure is maintained in solution and in the solid state. The reduction of 2 and 3 with LiAlH4 led to the formation of mixed tertiary/secondary chelating bis(phosphines) Acenap(PiPr(2))(PRH) (6 and 7), which were subsequently reacted with PtCl2(cod) to give the complexes [(6)/(7)PtCl2] (8 and 9). Reaction of 2 and 3 with a large excess of MeOTf at elevated temperature gave the chiral 1,2-diphosphoniums [Acenap(PiPr(2))(PRMe)](2+)([TfO](-))(2) (10 and 11), which were reduced with LiAlH4 to the heteroleptic bis(phosphines) Acenap(PiPr(2))(PRMe) (12 and 13); these were then reacted with [(nor)Mo(CO)(4)] to give the complexes [(12)/(13)Mo(CO)(4)] (14 and 15). The heteroleptic bis(phosphines) 6, 7, 12, and 13 display large through-space couplings (formally (4)J(PP) = 163-199 Hz), comparable in magnitude to (1)J(PP) couplings observed in phosphino-phosphonium salts 2-5 (303-412 Hz). Single-crystal X-ray structures of 2, 3, 7-9, 14, and 15 are reported.

  DOI：

  10.1021/om400259h
• 作为产物：
  描述：

  苯基二氯化磷 在 lithium aluminium tetrahydride 、 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 24.67h， 生成 [6-Di(propan-2-yl)phosphanyl-1,2-dihydroacenaphthylen-5-yl]-methyl-phenylphosphane
  参考文献：
  名称：

  peri-Substituted Phosphino-Phosphonium Salts: Synthesis and Reactivity

  摘要：

  The clean reaction of 5-lithio-6-(diisopropylphosphino)acenaphthene with dichlorophosphines RPCl2 gives the peri-substituted phosphino-phosphonium salts [Acenap(PiPr(2))(PR)]Cl-+(-) (2, R = Ph; 3, R = Fc; 4, R = NMe2; 5, R = iPr; Acenap = acenaphthene-5,6-diyl). Their ionic structure is maintained in solution and in the solid state. The reduction of 2 and 3 with LiAlH4 led to the formation of mixed tertiary/secondary chelating bis(phosphines) Acenap(PiPr(2))(PRH) (6 and 7), which were subsequently reacted with PtCl2(cod) to give the complexes [(6)/(7)PtCl2] (8 and 9). Reaction of 2 and 3 with a large excess of MeOTf at elevated temperature gave the chiral 1,2-diphosphoniums [Acenap(PiPr(2))(PRMe)](2+)([TfO](-))(2) (10 and 11), which were reduced with LiAlH4 to the heteroleptic bis(phosphines) Acenap(PiPr(2))(PRMe) (12 and 13); these were then reacted with [(nor)Mo(CO)(4)] to give the complexes [(12)/(13)Mo(CO)(4)] (14 and 15). The heteroleptic bis(phosphines) 6, 7, 12, and 13 display large through-space couplings (formally (4)J(PP) = 163-199 Hz), comparable in magnitude to (1)J(PP) couplings observed in phosphino-phosphonium salts 2-5 (303-412 Hz). Single-crystal X-ray structures of 2, 3, 7-9, 14, and 15 are reported.

  DOI：

  10.1021/om400259h