Diphenyl-trimethylsilylimino-[[tri(propan-2-yl)-lambda5-phosphanylidene]amino]-lambda5-phosphane | 348120-06-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Diphenyl-trimethylsilylimino-[[tri(propan-2-yl)-lambda5-phosphanylidene]amino]-lambda5-phosphane
• 英文别名: diphenyl-trimethylsilylimino-[[tri(propan-2-yl)-λ5-phosphanylidene]amino]-λ5-phosphane
• CAS: 348120-06-9
• 化学式: C₂₄H₄₀N₂P₂Si
• 分子量: 446.628
• InChiKey: OLVCTAUPOLTNEX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.01
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  三氯一茂钛 、 Diphenyl-trimethylsilylimino-[[tri(propan-2-yl)-lambda5-phosphanylidene]amino]-lambda5-phosphane 以 甲苯 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Phosphinimide−Phosphinimide Ligands:  New Bulky Ligands for Ethylene Polymerization Catalysts

  摘要：

  The phosphinimide-phosphines PPh2(NPR3) (R = i-Pr 1, t-Bu 2) were readily prepared; in 80-98% yield. These species react with AlMe3 or B(C6F5)(3) to form Me3AlPPh2(NPR3) (R = i-Pr 3, t-Bu 4) and (C6F5)(3)B(PPh2(NPi-Pr-3)) (5), respectively. Oxidation of compounds 1 and 2 with Me3SiN3 yields Me3SiNPPh2(NPR3) (R = i-Pr 6, t-Bu 7). These species react with CpTiCl3 to give titanium(IV) complexes CpTiCl2(NPPh2(NPR3) (R = i-Pr 8, t-Bu 9) and subsequently the alkylated complexes CpTiMe2(NPPh2(NPR3)) (R = i-Pr 10, t-Bu 11), Compounds 8-11 were tested for activity in ethylene polymerization. In the presence of excess methylalumoxane, the species 8 and 9 gave rise to active single-site catalysts, generating 299 and 34 gPE mmol(-1) h(-1), respectively. In contrast, activation of 10 and 11 by [Ph3C] [B(C6F5)(4)] showed negligible,polymerization activity. Reaction of 11 with B(C6F5)(3) was shown to give numerous products, one of which was the dicationic species [CpTi(mu -Cl)(NPPh2(NPt-Bu-3)](2) [BC6F5)(4)](2), 12. The formation of this species and the implications of these results for catalyst and ancillary ligand design are considered and discussed. X-ray crystallographic data are reported for 1, 3, 4, 8, and 12.

  DOI：

  10.1021/om0101184

文献信息

• Phosphinimide−Phosphinimide Ligands:  New Bulky Ligands for Ethylene Polymerization Catalysts
  作者：Nancy L. S. Yue、Douglas W. Stephan

  DOI：10.1021/om0101184

  日期：2001.5.1

  The phosphinimide-phosphines PPh2(NPR3) (R = i-Pr 1, t-Bu 2) were readily prepared; in 80-98% yield. These species react with AlMe3 or B(C6F5)(3) to form Me3AlPPh2(NPR3) (R = i-Pr 3, t-Bu 4) and (C6F5)(3)B(PPh2(NPi-Pr-3)) (5), respectively. Oxidation of compounds 1 and 2 with Me3SiN3 yields Me3SiNPPh2(NPR3) (R = i-Pr 6, t-Bu 7). These species react with CpTiCl3 to give titanium(IV) complexes CpTiCl2(NPPh2(NPR3) (R = i-Pr 8, t-Bu 9) and subsequently the alkylated complexes CpTiMe2(NPPh2(NPR3)) (R = i-Pr 10, t-Bu 11), Compounds 8-11 were tested for activity in ethylene polymerization. In the presence of excess methylalumoxane, the species 8 and 9 gave rise to active single-site catalysts, generating 299 and 34 gPE mmol(-1) h(-1), respectively. In contrast, activation of 10 and 11 by [Ph3C] [B(C6F5)(4)] showed negligible,polymerization activity. Reaction of 11 with B(C6F5)(3) was shown to give numerous products, one of which was the dicationic species [CpTi(mu -Cl)(NPPh2(NPt-Bu-3)](2) [BC6F5)(4)](2), 12. The formation of this species and the implications of these results for catalyst and ancillary ligand design are considered and discussed. X-ray crystallographic data are reported for 1, 3, 4, 8, and 12.